Silicone hydrogel contact lenses

ABSTRACT

The present invention generally relates to inherently wettable silicone hydrogel contact lenses having relatively high oxygen permeability, relatively high equilibrium water content and relatively low elastic modulus. The present invention is also related to a method for making such inherently wettable silicone hydrogel contact lenses.

This application is a continuation of application Ser. No. 16/000,933filed 6 Jun. 2018, now U.S. Pat. No. 10,875,967, which claims thebenefit under 35 USC § 119 (e) of U.S. provisional application No.62/516,215 filed 7 Jun. 2017, herein incorporated by reference in itsentirety.

The present invention generally relates to silicone hydrogel contactlenses having an inherently wettable surface and to a method forproducing the same.

BACKGROUND

Silicone hydrogel (SiHy) contact lenses, which are made of a hydrated,crosslinked polymeric material that contains silicone and a certainamount of water within the lens polymer matrix at equilibrium, areincreasingly becoming popular, because they have minimal adverse effectson corneal health due to their high oxygen permeability. But,incorporation of silicone in a contact lens material can haveundesirable effects on the hydrophilicity and wettability of SiHycontact lenses, because silicon is hydrophobic and has a great tendencyto migrate onto the lens surface being exposed to air. Contact lensesmanufacturers have made a great effort in developing SiHy contact lenseshaving a hydrophilic and wettable surface.

One approach for modifying the hydrophilicity and wettability of a SiHycontact lens is through the use of a plasma treatment, for example,commercial lenses, such as AIR OPTIX® (Alcon), PremiO™ (Menicon), andPUREVISION™ (Bausch & Lomb), utilize this approach in their productionprocesses. Although a plasma coating is durable and can provide anadequate hydrophilicity/wettability, plasma treatment of SiHy contactlenses may not be cost effective, because the preformed SiHy contactlenses must typically be dried before plasma treatment and because ofrelative high capital investment associated with plasma treatmentequipment.

Another approach is to attach hydrophilic polymers onto the SiHy contactlens according to various mechanisms (see for example, U.S. Pat. Nos.6,099,122, 6,436,481, 6,440,571, 6,447,920, 6,465,056, 6,521,352,6,586,038, 6,623,747, 6,730,366, 6,734,321, 6,835,410, 6,878,399,6,923,978, 6,440,571, and 6,500,481, U.S. Pat. Appl. Pub. Nos.2009-0145086 A1, 2009-0145091 A1, 2008-0142038 A1, and 2007-0122540 A1).Although those techniques can be use in rendering a SiHy contact lenswettable, they may not be cost-effective and/or time-efficient forimplementation in a mass production environment, because they typicallyrequire relatively long time and/or involve laborious, multiple steps toobtain a hydrophilic coating.

Another approach is a layer-by-layer (LbL) polyionic material depositiontechnique (see, e.g., U.S. Pat. Nos. 6,451,871, 6,719,929, 6,793,973,6,884,457, 6,896,926, 6,926,965, 6,940,580, 7,297,725, 8,044,112,7,858,000, and 8,158,192). Although the LbL deposition technique canprovide a cost effective process for rendering a SiHy contact lenswettable, LbL coatings may not be as durable as plasma coatings and mayhave relatively high densities of surface charges; which may interferewith contact lens cleaning and disinfecting solutions. To improve thedurability, crosslinking of LbL coatings on contact lenses has beenproposed in U.S. Pat. Nos. 8,147,897 and 8,142,835. However, crosslinkedLbL coatings may have a hydrophilicity and/or wettability inferior thanoriginal LbL coatings (prior to crosslinking) and still have relativehigh densities of surface charges.

Recently, a new approach has been described in U.S. Pat. No. 8,529,057for applying a non-silicone hydrogel coating onto a SiHy contact lensdirectly in a lens package during autoclave (sterilization). Althoughthis new approach can provide silicone hydrogel contact lenses withdurable hydrophilic coatings thereon, it may not be environmentallyfriendly manufacturing process because it involves use of organicsolvents in lens processing steps after the lens molding step.

Another approach is the incorporation of preformed hydrophilic polymersas polymeric wetting agents in a lens formulation for making SiHycontact lens as proposed in U.S. Pat. Nos. 6,367,929, 6,822,016,7,052,131, and 7,249,848. This method may not require additionalprocesses for modifying the hydrophilicity and wettability of SiHycontact lenses after cast-molding. However, polymeric wetting agents maynot be compatible with the silicone components in the lens formulationand the incompatibility may impart haziness to the resultant lenses.Further, such surface treatment may not provide a durable surface forextended wear purposes.

A further approach is the incorporation of monomeric wetting agents(e.g., N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, or the like) in alens formulation for making SiHy contact lens as proposed in U.S. Pat.Nos. 6,867,245, 7,268,198, 7,540,609, 7,572,841, 7,750,079, 7,934,830,8,231,218, 8,367,746, 8,445,614, 8,481,662, 8,487,058, 8,513,325,8,703,891, 8,820,928, 8,865,789, 8,937,110, 8,937,111, 9,057,821,9,057,822, 9,121,998, 9,125,808, 9,140,825, 9,140,908, 9,156,934,9,164,298, 9,170,349, 9,188,702, 9,217,813, 9,296,159, 9,322,959,9,322,960, 9,360,594, 9,529,119. Commercial SiHy contact lenses, suchas, Biofinity® (CooperVision, Dk=128 barrers, 48% H₂O), Avaira®(CooperVision, Dk=100 barrers, 46% H₂O), Clariti® (CooperVision, Dk=60barrers, 56% H₂O), MyDay® (CooperVision, Dk=80 barrers, 54% H₂O), ULTRA™(Bausch & Lamb, Dk=114 barrers, 46% H₂O), may utilize this approach intheir production processes. Although this approach might be used in thecommercial SiHy lens production to provide fresh (unused) SiHy lenseswith adequately hydrophilic surfaces, there are some limitations. Forexample, the higher oxygen permeability of a SiHy contact lens could beachieved according to this approach, but at the expense of itsequilibrium water content and atomic Si percentage at lens surface.Typically, relatively-lower equilibrium water content andrelatively-higher atomic Si percentage go with higher oxygenpermeability in tandem. Further, it may also have one or more of thefollowing disadvantages: slightly-high haziness due to theincompatibility of polymerizable silicone components with monomericwetting agents and other hydrophilic components; higher surface siliconecontents; susceptibility to form dry spots and/or hydrophobic surfaceareas created due to air exposure, dehydrating-rehydrating cycles,shearing forces of the eyelids, silicone migration to the surface,and/or partial failure to prevent silicone from exposure; andnot-adequate lubricity.

SUMMARY OF THE INVENTION

The invention, in one aspect, provides a silicone hydrogel contact lens,comprising a silicone hydrogel bulk material which comprises (1) firstrepeating units of at least one siloxane-containing vinylic monomerhaving 0 to 10 first H-donor moieties, (2) second repeating units of atleast one first polysiloxane vinylic crosslinker which has a numberaverage molecular weight of from about 3000 Daltons to about 80,000Daltons and comprises (a) two terminal (meth)acryloyl groups, (b) atleast one polysiloxane segment comprising dimethylsiloxane units andhydrophilized siloxane units each having one methyl substituent and onemonovalent C₄-C₄₀ organic radical substituent having one or more secondH-donor moieties, and (c) from 0 to 20 third H-donor moieties which areintegral parts of molecular structures outside of the polysiloxanesegment, (3) third repeating units of at least one hydrophilic N-vinylamide monomer, and (4) optionally fourth repeating units of at least onesecond polysiloxane vinylic crosslinker having 0 to 35 fourth H-donormoieties, wherein the first and second polysiloxane vinylic crosslinkersare different from each other, wherein the first, second, third andfourth H-donor moieties independent of one another are hydroxyl groups,carboxyl groups, amino groups of —NHR^(o), amino linkages of —NH—, amidelinkages of —CONH—, urethane linkages of —OCONH—, or combinationsthereof, wherein R^(o) is H or a C₁-C₄ alkyl, wherein the siliconehydrogel bulk material comprises at least 8.8 mmole of the thirdrepeating units per gram of all the first, second and fourth repeatingunits in total and at least 0.11 meqs of all the first, second, thirdand fourth H-donor moieties in total per gram of the third repeatingunits, wherein the silicone hydrogel contact lens has an oxygenpermeability of at least 50 barrers, an elastic modulus of from about0.2 MPa to about 1.5 MPa, and an equilibrium water content of from about40% to about 70% and is inherently wettable as characterized by having awater-break-up-time of at least 10 seconds and a water contact angle bycaptive bubble of about 80 degrees or less without being subjected toany post-curing surface treatment.

In another aspect, the present invention provides a method for producinginherently-wettable silicone hydrogel contact lenses. The methodcomprises the steps of: preparing a polymerizable composition which isclear at room temperature and optionally but preferably at a temperatureof from about 0 to about 4° C., wherein the polymerizable compositioncomprises (a) at least one siloxane-containing vinylic monomer having 0to 10 first H-donor moieties, (b) at least one first polysiloxanevinylic crosslinker which has a number average molecular weight of fromabout 3000 Daltons to about 80,000 Daltons and comprises (i) twoterminal (meth)acryloyl groups, (ii) at least one polysiloxane segmentcomprising dimethylsiloxane units and hydrophilized siloxane units eachhaving one methyl substituent and one monovalent C₄-C₄₀ organic radicalsubstituent having one or more second H-donor moieties, and (iii) from 0to 20 third H-donor moieties which are integral parts of molecularstructures outside of the polysiloxane segment, (c) at least onehydrophilic N-vinyl amide monomer, (d) optionally at least one secondpolysiloxane vinylic crosslinker having 0 to 35 fourth H-donor moieties,and (e) at least one free radical initiator, wherein the first andsecond polysiloxane vinylic crosslinker are different from each other,wherein the first, second, third and fourth H-donor moieties independentof one another are hydroxyl groups, carboxyl groups, amino groups of—NHR^(o), amino linkages of —NH—, amide linkages of —CONH—, urethanelinkages of —OCONH—, or combinations thereof, wherein R^(o) is H or aC₁-C₄ alkyl, wherein the polymerizable composition comprises at least8.8 mmoles of component (c) per gram of all components (a), (b) and (d)in total and at least 0.11 meqs of the first, second, third and fourthH-donor moieties in total per gram of component (c); introducing thepolymerizable composition into a lens mold; curing thermally oractinically the polymerizable composition in the lens mold to form asilicone hydrogel contact lens, wherein the silicone hydrogel contactlens has an oxygen permeability of at least 50 barrers, an elasticmodulus of from about 0.2 MPa to about 1.5 MPa, and an equilibrium watercontent of from about 40% to about 70% and is inherently wettable ascharacterized by having a water-break-up-time of at least 10 seconds anda water contact angle by captive bubble of about 80 degrees or lesswithout being subjected to any post-curing surface treatment.

These and other aspects of the invention will become apparent from thefollowing description of the presently preferred embodiments. Thedetailed description is merely illustrative of the invention and doesnot limit the scope of the invention, which is defined by the appendedclaims and equivalents thereof.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 schematically shows how to measure water-break-up time of acontact lens.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Generally, the nomenclatureused herein and the laboratory procedures are well known and commonlyemployed in the art. Conventional methods are used for these procedures,such as those provided in the art and various general references. Wherea term is provided in the singular, the inventors also contemplate theplural of that term. The nomenclature used herein and the laboratoryprocedures described below are those well-known and commonly employed inthe art. Also, as used in the specification including the appendedclaims, reference to singular forms such as “a,” “an,” and “the” includethe plural, and reference to a particular numerical value includes atleast that particular value, unless the context clearly dictatesotherwise. “About” as used herein means that a number referred to as“about” comprises the recited number plus or minus 1-10% of that recitednumber.

“Contact Lens” refers to a structure that can be placed on or within awearer's eye. A contact lens can correct, improve, or alter a user'seyesight, but that need not be the case. A contact lens can be of anyappropriate material known in the art or later developed, and can be asoft lens, a hard lens, or a hybrid lens. A “silicone hydrogel contactlens” refers to a contact lens comprising a silicone hydrogel bulk(core) material.

A “soft contact lens” refers to a contact lens which has an elasticmodulus (i.e., Young's modulus) of less than 2.5 MPa.

A “hydrogel” or “hydrogel material” refers to a crosslinked polymericmaterial which has three-dimensional polymer networks (i.e., polymermatrix), is insoluble in water, but can hold at least 10 percent byweight of water in its polymer matrix when it is fully hydrated.

A “silicone hydrogel” refers to a silicone-containing hydrogel obtainedby copolymerization of a polymerizable composition comprising at leastone silicone-containing monomer or at least one silicone-containingmacromer or at least one crosslinkable silicone-containing prepolymer.

As used in this application, the term “non-silicone hydrogel” refers toa hydrogel that is theoretically free of silicon.

“Hydrophilic,” as used herein, describes a material or portion thereofthat will more readily associate with water than with lipids.

A “vinylic monomer” refers to a compound that has one sole ethylenicallyunsaturated group, is soluble in a solvent, and can be polymerizedactinically or thermally.

The term “room temperature” refers to a temperature of about 21° C. toabout 27° C.

The term “soluble”, in reference to a compound or material in a solvent,means that the compound or material can be dissolved in the solvent togive a solution with a concentration of at least about 0.02% by weightat room temperature.

The term “insoluble”, in reference to a compound or material in asolvent, means that the compound or material can be dissolved in thesolvent to give a solution with a concentration of less than 0.005% byweight at room temperature.

As used in this application, the term “ethylenically unsaturated group”is employed herein in a broad sense and is intended to encompass anygroups containing at least one >C═C<group. Exemplary ethylenicallyunsaturated groups include without limitation (meth)acryloyl

allyl, vinyl, styrenyl, or other C═C containing groups.

The term “terminal (meth)acryloyl group” refers to one (meth)acryloylgroup at one of the two ends of the main chain (or backbone) of anorganic compound as known to a person skilled in the art.

The term “(meth)acrylamide” refers to methacrylamide and/or acrylamide.

The term “(meth)acrylate” refers to methacrylate and/or acrylate.

As used herein, “actinically” in reference to curing, crosslinking orpolymerizing of a polymerizable composition, a prepolymer or a materialmeans that the curing (e.g., crosslinked and/or polymerized) isperformed by actinic irradiation, such as, for example, UV/visibleirradiation, ionizing radiation (e.g. gamma ray or X-ray irradiation),microwave irradiation, and the like. Thermal curing or actinic curingmethods are well-known to a person skilled in the art.

A “hydrophilic vinylic monomer”, as used herein, refers to a vinylicmonomer which as a homopolymer typically yields a polymer that iswater-soluble or can absorb at least 10 percent by weight of water.

A “hydrophobic vinylic monomer”, as used herein, refers to a vinylicmonomer which as a homopolymer typically yields a polymer that isinsoluble in water and can absorb less than 10 percent by weight ofwater.

A “blending vinylic monomer” refers to a vinylic monomer capable ofdissolving both hydrophilic and hydrophobic components of apolymerizable composition to form a solution.

An “acrylic monomer” refers to a vinylic monomer having one sole(meth)acryloyl group.

An “N-vinyl amide monomer” refers to an amide compound having a vinylgroup (—CH═CH₂) that is directly attached to the nitrogen atom of theamide group.

A “macromer” or “prepolymer” refers to a compound or polymer thatcontains ethylenically unsaturated groups and has a number averagemolecular weight of greater than 700 Daltons.

As used in this application, the term “vinylic crosslinker” refers to anorganic compound having at least two ethylenically unsaturated groups. A“vinylic crosslinking agent” refers to a vinylic crosslinker having amolecular weight of 700 Daltons or less.

As used in this application, the term “polymer” means a material formedby polymerizing/crosslinking one or more monomers or macromers orprepolymers or combinations thereof.

As used in this application, the term “molecular weight” of a polymericmaterial (including monomeric or macromeric materials) refers to thenumber average molecular weight unless otherwise specifically noted orunless testing conditions indicate otherwise.

A “polysiloxane segment” refers to a polymer chain consisting of atleast three consecutively- and directly-linked siloxane units (divalentradical) each independent of one another having a formula of

in which R₁′ and R₂′ are two substituents independently selected fromthe group consisting of C₁-C₁₀ alkyl, C₁-C₄ alkyl- orC₁-C₄-alkoxy-substituted phenyl, C₁-C₁₀ fluoroalkyl, C₁-C₁₀ fluoroether,C₆-C₁₈ aryl radical, -alk-(OC₂H₄)_(γ1)—OR^(o) (in which alk is C₁-C₆alkyl diradical, R^(o) is H or C₁-C₄ alkyl and γ1 is an integer from 1to 10), a C₂-C₄₀ organic radical having at least one functional groupselected from the group consisting of hydroxyl group (—OH), carboxylgroup (—COOH), —NR₃′R₄′, amino linkages of —NR₃′—, amide linkages of—CONR₃′—, amide of —CONR₃′R₄′, urethane linkages of —OCONH—, and C₁-C₄alkoxy group, or a linear hydrophilic polymer chain, in which R₃′ andR₄′ independent of each other are hydrogen or a C₁-C₁₅ alkyl.

A “polysiloxane vinylic crosslinker” refers to a compound comprising atleast one polysiloxane segment and at least twoethylenically-unsaturated groups.

A “linear polysiloxane vinylic crosslinker” refers to a compoundcomprising a main chain which includes at least one polysiloxane segmentand is terminated with one ethylenically-unsaturated group at each ofthe two ends of the main chain.

A “chain-extended polysiloxane vinylic crosslinker” refers to a compoundcomprising at least two ethylenically-unsaturated groups and at leasttwo polysiloxane segments each pair of which are linked by one divalentradical.

The term “fluid” as used herein indicates that a material is capable offlowing like a liquid.

As used in this application, the term “clear” in reference to apolymerizable composition means that the polymerizable composition is atransparent solution or liquid mixture (i.e., having a lighttransmissibility of 85% or greater, preferably 90% or greater in therange between 400 to 700 nm).

The term “alkyl” refers to a monovalent radical obtained by removing ahydrogen atom from a linear or branched alkane compound. An alkyl group(radical) forms one bond with one other group in an organic compound.

The term “alkylene divalent group” or “alkylene diradical” or “alkyldiradical” interchangeably refers to a divalent radical obtained byremoving one hydrogen atom from an alkyl. An alkylene divalent groupforms two bonds with other groups in an organic compound.

The term “alkoxy” or “alkoxyl” refers to a monovalent radical obtainedby removing the hydrogen atom from the hydroxyl group of a linear orbranched alkyl alcohol. An alkoxy group (radical) forms one bond withone other group in an organic compound.

In this application, the term “substituted” in reference to an alkyldiradical or an alkyl radical means that the alkyl diradical or thealkyl radical comprises at least one substituent which replaces onehydrogen atom of the alkyl diradical or the alkyl radical and isselected from the group consisting of hydroxyl (—OH), carboxyl (—COOH),—NH₂, sulfhydryl (—SH), C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio(alkyl sulfide), C₁-C₄ acylamino, C₁-C₄ alkylamino, di-C₁-C₄ alkylamino,and combinations thereof.

A free radical initiator can be either a photoinitiator or a thermalinitiator. A “photoinitiator” refers to a chemical that initiates freeradical crosslinking/polymerizing reaction by the use of light. A“thermal initiator” refers to a chemical that initiates radicalcrosslinking/polymerizing reaction by the use of heat energy.

The intrinsic “oxygen permeability”, Dk_(i), of a material is the rateat which oxygen will pass through a material. As used in thisapplication, the term “oxygen permeability (Dk)” in reference to ahydrogel (silicone or non-silicone) or a contact lens means a correctedoxygen permeability (Dk_(c)) which is measured at about 34-35° C. andcorrected for the surface resistance to oxygen flux caused by theboundary layer effect according to the procedures described in Example 1of U.S. Pat. Appl. Pub. No. 2012-0026457 A1. Oxygen permeability isconventionally expressed in units of barrers, where “barrer” is definedas [(cm³ oxygen)(mm)/(cm²)(sec)(mm Hg)]×10⁻¹⁰.

The “oxygen transmissibility”, Dk/t, of a lens or material is the rateat which oxygen will pass through a specific lens or material with anaverage thickness of t [in units of mm] over the area being measured.Oxygen transmissibility is conventionally expressed in units ofbarrers/mm, where “barrers/mm” is defined as [(cm³ oxygen)/(cm²)(sec)(mmHg)]×10⁻⁹.

“Ophthalmically compatible”, as used herein, refers to a material orsurface of a material which may be in intimate contact with the ocularenvironment for an extended period of time without significantlydamaging the ocular environment and without significant user discomfort.

The term “modulus” or “elastic modulus” in reference to a contact lensor a material means the tensile modulus or Young's modulus which is ameasure of the stiffness of a contact lens or a material. A personskilled in the art knows well how to determine the elastic modulus of asilicone hydrogel material or a contact lens. For example, allcommercial contact lenses have reported values of elastic modulus. Itcan be measured as described in Example 1.

“UVA” refers to radiation occurring at wavelengths between 315 and 380nanometers; “UVB” refers to radiation occurring between 280 and 315nanometers; “Violet” refers to radiation occurring at wavelengthsbetween 380 and 440 nanometers.

“UVA transmittance” (or “UVA % T”), “UVB transmittance” or “UVB % T”,and “violet-transmittance” or “Violet % T” are calculated by thefollowing formula

${{UVA}\mspace{14mu}\% T} = {\frac{\begin{matrix}{{Average}\mspace{14mu}\%\mspace{14mu}{Transmission}\mspace{14mu}{between}} \\{315\mspace{14mu}{nm}\mspace{14mu}{and}\mspace{14mu} 380\mspace{14mu}{nm}}\end{matrix}}{{Luminescence}\mspace{14mu}\% T} \times 100}$${{UVB}\mspace{14mu}\% T} = {\frac{\begin{matrix}{{Average}\mspace{14mu}\%\mspace{14mu}{Transmission}\mspace{14mu}{between}} \\{280\mspace{14mu}{nm}\mspace{14mu}{and}\mspace{14mu} 315\mspace{14mu}{nm}}\end{matrix}}{{Luminescence}\mspace{14mu}\% T} \times 100}$${{Violet}\mspace{14mu}\% T} = {\frac{\begin{matrix}{{Average}\mspace{14mu}\%\mspace{14mu}{Transmission}\mspace{14mu}{between}} \\{380\mspace{14mu}{nm}\mspace{14mu}{and}\mspace{14mu} 440\mspace{14mu}{nm}}\end{matrix}}{{Luminescence}\mspace{14mu}\% T} \times 100}$in which Luminescence % T is determined by the following formulaLuminescence % T=Average % Transmission between 780-380 nm.

An “H-donor moiety” refers to a functional group which comprises ahydrogen atom capable of forming a hydrogen bond with another functionalgroup. Examples of H-donor moieties include without limitation hydroxylgroup, amide group of —CONHR^(o), amide linkage of —CONH—, urethanelinkage of —OCONH—, urea linkage of —HNCONH—, carboxyl group of —COOH,amino groups of —NHR^(o), amino linkages of —NH—, and combinationsthereof, wherein R^(o) is H or a C₁-C₄ alkyl.

The term “inherently wettable” in reference to a silicone hydrogelcontact lens means that the silicone hydrogel has water-break-up-time(WBUT) of about 10 seconds or more and a water contact angle by captivebubble (WCA_(cb)) of about 80 degree or less without being subjected toany surface treatment after the silicone hydrogel contact lens is formedby thermally or actinically polymerizing (i.e., curing) a siliconehydrogel lens formulation. In accordance with the invention, WBUT andWCA_(cb) are measured according to the procedures described in Example1.

“Surface modification” or “surface treatment”, as used herein, meansthat an article has been treated in a surface treatment process (or asurface modification process) prior to or posterior to the formation ofthe article, in which (1) a coating is applied to the surface of thearticle, (2) chemical species are adsorbed onto the surface of thearticle, (3) the chemical nature (e.g., electrostatic charge) ofchemical groups on the surface of the article are altered, or (4) thesurface properties of the article are otherwise modified. Exemplarysurface treatment processes include, but are not limited to, a surfacetreatment by energy (e.g., a plasma, a static electrical charge,irradiation, or other energy source), chemical treatments, the graftingof hydrophilic vinylic monomers or macromers onto the surface of anarticle, mold-transfer coating process disclosed in U.S. Pat. No.6,719,929, the incorporation of wetting agents into a lens formulationfor making contact lenses proposed in U.S. Pat. Nos. 6,367,929 and6,822,016, reinforced mold-transfer coating disclosed in U.S. Pat. No.7,858,000, and a hydrophilic coating composed of covalent attachment orphysical deposition of one or more layers of one or more hydrophilicpolymer onto the surface of a contact lens disclosed in U.S. Pat. Nos.8,147,897 and 8,409,599 and US Pat. Appl. Pub. Nos. 2011-0134387 A1,2012-0026457 A1 and 2013-0118127 A1.

“Post-curing surface treatment”, in reference to a silicone hydrogelbulk material or a SiHy contact lens, means a surface treatment processthat is performed after the silicone hydrogel bulk material or the SiHycontact lens is formed by curing (i.e., thermally or actinicallypolymerizing) a SiHy lens formulation. A “SiHy lens formulation” refersto a polymerizable composition that comprises all necessarypolymerizable components for producing a SiHy contact lens or a SiHylens bulk material as well known to a person skilled in the art.

The invention is generally related to inherently-wettable SiHy contactlenses with a relatively high oxygen permeability, a desired watercontent (e.g., from about 40% to about 70% by weight), and a relativelylow elastic modulus (e.g., from about 0.2 MPa to about 1.5 MPa). Thisinvention is partly based on the surprise discovery thatinherently-wettable SiHy contact lenses can be formed from a SiHy lensformulation (i.e., a polymerizable composition) that comprises apolysiloxane vinylic crosslinker (“Di-PDMS”) having H-donor moieties(“H-D”), a siloxane-containing vinylic monomer (“mono-PDMS”) with orwithout H-donor moieties, a N-vinyl amide monomer (“NVA”) (e.g.,N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, or the like), andoptionally other silicone-containing polymerizable component(s) with orwithout H-donor moieties, provided that the SiHy lens formulationcomprise about 8.8 mmoles or more of all N-vinyl amide monomer(s)(“NVA”) per gram of all the silicone-containing polymerizable components

$( {{i.e.},{\frac{\lbrack{NVA}\rbrack\mspace{14mu}{mmole}}{( {\lbrack {{mono}\text{-}{PDMS}} \rbrack + \lbrack {{di}\text{-}{PDMS}} \rbrack} )\mspace{14mu} g} = {8.8\mspace{14mu}{mmole}\text{/}g}}} )$and about 0.11 miliequivalents (“meq”) or more of the H-donor moietiesper gram of all N-vinyl amide monomer(s)

$( ( {{i.e.},{\frac{\lbrack {H\text{-}D} \rbrack\mspace{14mu}{meq}}{\lbrack{NVA}\rbrack\mspace{14mu} g} = {0.11\mspace{14mu}{meq}\text{/}g}}} ) ),$which are contributed from the polysiloxane vinylic crosslinker and thesiloxane-containing vinylic monomer, per gram of the N-vinyl amidemonomer. The resultant SiHy lenses not only can be inherently wettable,but also can have a combination of the desired contact lens propertiesincluding relatively high oxygen permeability, relatively high watercontent, relatively low modulus, and relatively-low surface atomic Sipercentage.

The invention, in one aspect, provides a silicone hydrogel contact lens,comprising a silicone hydrogel bulk material which comprises (1) firstrepeating units of at least one siloxane-containing vinylic monomerincluding 0 to 10 first H-donor moieties, (2) second repeating units ofat least one first polysiloxane vinylic crosslinker which has a numberaverage molecular weight of from about 3000 Daltons to about 80,000Daltons and comprises (a) two terminal (meth)acryloyl groups, (b) atleast one polysiloxane segment comprising dimethylsiloxane units andhydrophilized siloxane units each having one methyl substituent and onemonovalent C₄-C₄₀ organic radical substituent having one or more secondH-donor moieties, and (c) from 0 to 20 third H-donor moieties which areintegral parts of molecular structures outside of the polysiloxanesegment, (3) third repeating units of at least one hydrophilic N-vinylamide monomer, and (4) optionally fourth repeating units of at least onesecond polysiloxane vinylic crosslinker having 0 to 35 fourth H-donormoieties, wherein the first and second polysiloxane vinylic crosslinkersare different from each other, wherein the first, second, third andfourth H-donor moieties independent of one another are hydroxyl groups,carboxyl groups, amino groups of —NHR^(o) in which R^(o) is H or a C₁-C₄alkyl, amino linkages of —NH—, amide linkages of —CONH—, urethanelinkages of —OCONH—, or combinations thereof, wherein the siliconehydrogel bulk material comprises at least 8.8 (preferably at least 9.0,more preferably at least 9.2, even more preferably at least 9.6) mmolesof the third repeating units per gram of all the first, second andfourth repeating units in total and at least 0.11 (preferably at least0.15, more preferably at least 0.20, even more preferably at least 0.25)meqs of all the first, second, third and fourth H-donor moieties intotal per gram of the third repeating units, wherein the siliconehydrogel contact lens has an oxygen permeability of at least 50 barrers,an elastic modulus of from about 0.2 MPa to about 1.5 MPa, and anequilibrium water content of from about 40% to about 70% and isinherently wettable as characterized by having a water-break-up-time ofat least 10 seconds (preferably at least 15 seconds, more preferably atleast 20 seconds) and a water contact angle by captive bubble of about80 degrees or less (preferably about 75 degrees or less, more preferablyabout 70 degrees or less, even more preferably about 65 degrees or less)without being subjected to any post-curing surface treatment.

In accordance with the invention, the amounts (weight, mmole, and meq)of the first, second, third and fourth repeating units as well as theH-donor moieties are calculated based on the amounts of said at leastone siloxane-containing vinylic monomer, said at least one firstpolysiloxane vinylic crosslinker, said at least one N-vinyl amidemonomer and said at least one second polysiloxane vinylic crosslinkerpresent in a polymerizable composition for making a silicone hydrogelcontact lens of the invention. It should be understood that if anypre-formed homopolymer or copolymer of an N-vinyl amide monomer ispresent in the polymerizable composition prior to cast molding, then therepeating units of such an N-vinyl amide monomer in the preformedhomopolymer or copolymer must not be included in the calculations of theamounts (weight, mmole, and meq) of the first, second, third and fourthrepeating units as well as the H-donor moieties.

Any suitable siloxane-containing vinylic monomers can be used in theinvention. One class of preferred siloxane containing vinylic monomersis mono-(meth)acryloyl-terminated, monoalkyl-terminated polysiloxanes.In a more preferred embodiment, the siloxane-containing vinylic monomeris a mono-(meth)acryloyl-terminated, monoalkyl-terminated polysiloxaneof formula (I)

in which:R_(o) is H or methyl; X_(o) is O or NR₁; L₁ is a C₃-C₈ alkylene divalentradical or a divalent radical of

L₁′ is a C₂-C₈ alkylene divalent radical which has zero or one hydroxylgroup; L₁″ is C₃-C₈ alkylene divalent radical which has zero or onehydroxyl group; X₁ is O, NR₁, NHCOO, OCONH, CONR₁, or NR₁CO; R₁ is H ora C₁-C₄ alkyl having 0 to 2 hydroxyl group; R_(t1) is a C₁-C₄ alkyl; X₁′is O or NR₁; q1 is an integer of 1 to 20; q2 is an integer of 0 to 20;n1 is an integer of 3 to 25.

Examples of mono-(meth)acryloyl-terminated, monoalkyl-terminatedpolysiloxanes of formula (I) include without limitationα-(meth)acryloxypropyl terminated ω-butyl (or ω-methyl) terminatedpolydimethylsiloxane, α-(meth)acryloxy-2-hydroxypropyloxypropylterminated ω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(2-hydroxyl-methacryloxypropyloxypropyl)-ω-butyl-decamethylpentasiloxane,α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxy-propyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxy-butylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(meth)acryloxy(polyethylenoxy)-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-terminated ω-butyl (orω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyloxy-(polyethylenoxy)propyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(meth)acryloylamidopropyloxypropyl terminated ω-butyl (or ω-methyl)terminated polydimethylsiloxane,α-N-methyl-(meth)acryloylamidopropyloxypropyl terminated ω-butyl (orω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxy-propyl]-terminatedω-butyl (or ω-methyl) polydimethylsiloxane,α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloylamido-2-hydroxypropyloxypropyl] terminated ω-butyl(or ω-methyl) polydimethylsiloxane,α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl] terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,N-methyl-N′-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide,N-(2,3-dihydroxypropane)-N′-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide,(meth)acryloylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane, andmixtures thereof. Mono-(meth)acryloyl-terminated, monoalkyl-terminatedpolysiloxanes of formula (I) can be obtained from commercial suppliers(e.g., Shin-Etsu, Gelest, etc.) or prepared according to proceduresdescribed in U.S. Pat. Nos. 6,867,245, 8,415,405, 8,475,529, 8,614,261,and 9,217,813 or by reacting a hydroxyalkyl (meth)acrylate or(meth)acrylamide or a (meth)acryloxypolyethylene glycol with amono-epoxypropyloxypropyl-terminated polydimethylsiloxane, by reactingglycidyl (meth)acrylate with a mono-carbinol-terminatedpolydimethylsiloxane, a mono-aminopropyl-terminatedpolydimethylsiloxane, or a mono-ethylaminopropyl-terminatedpolydimethylsiloxane, ob by reacting isocyanatoethyl (meth)acrylate witha mono-carbinol-terminated polydimethylsiloxane according to couplingreactions well known to a person skilled in the art.

Another class of preferred siloxane containing vinylic monomers isvinylic monomers containing a tris(trimethylsilyloxy)silyl orbis(trimethylsilyloxy)alkylsilyl group (i.e.,tris(trimethylsilyloxy)silyl-containing vinylic monomer orbis(trimethylsilyloxy)alkylsilyl-containing vinylic monomer. In a morepreferred embodiment, the siloxane-containing vinylic monomer is atris(trimethylsilyloxy)silyl-containing orbis(trimethylsilyloxy)alkylsilyl-containing vinylic monomer of formula(II)

in which: R_(o) is H or methyl; X_(o) is O or NR₁; L₂ is a C₃-C₈alkylene divalent radical or a divalent radical of or -L₂′-X₂-L₂″-,—(C₂H₄O)_(q1)-L₂″-, —(C₂H₄O)_(q1)—CONH-L₂″-; or-L₂′—NHCOO—(C₂H₄O)_(q1)-L₂″-, L₂′ is a C₂-C₈ alkylene divalent radicalwhich has zero or one hydroxyl group; L₂″ is C₃-C₈ alkylene divalentradical which has zero or one hydroxyl group; X₁ is O, NR₁, NHCOO,OCONH, CONR₁, or NR₁CO; R₁ is H or a C₁-C₄ alkyl having 0 to 2 hydroxylgroup; R₁₂ is a C₁-C₄ alkyl; q1 is an integer of 1 to 20, r1 is aninteger of 2 or 3.

Examples of preferred siloxane-containing vinylic monomers of formula(II) include without limitation tris(trimethylsilyloxy)silylpropyl(meth)acrylate,[3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane,[3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane,3-(meth)acryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane,N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl(meth)acrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)(meth)acrylamide,N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide,N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)(meth)acrylamide, and mixtures thereof. Preferred siloxane-containingvinylic monomers of formula (II) can be obtained from commercialsuppliers or can be prepared according to procedures described in U.S.Pat. Nos. 7,214,809, 8,475,529, 8,658,748, 9,097,840, 9,103,965, and9,475,827.

In accordance with the present invention, the siloxane-containingvinylic monomer is a mono-(meth)acryloyl-terminated monoalkyl-terminatedpolysiloxane, a bis(trimethylsilyloxy)-alkylsilyl-containing vinylicmonomer, tris(trimethylsilyloxy)silyl-containing vinylic monomer, ormixtures thereof, preferably a mono-(meth)acryloyl-terminatedmonoalkyl-terminated polysiloxane, abis(trimethylsilyloxy)alkylsilyl-containing vinylic monomer orcombinations thereof, more preferably a mono-(meth)acryloyl-terminatedmonoalkyl-terminated polysiloxane having a weight-average molecularweight of about 2500 Daltons or less (preferably about 2000 Daltons orless, more preferably about 1700 Daltons or less, even more preferablyfrom about 450 to about 1500 Daltons) of formula (I), even morepreferably more preferably a mono-(meth)acryloyl-terminatedmonoalkyl-terminated polysiloxane of formula (I) in which n1 is aninteger of 3 to 25 (preferably 3 to 20, more preferably 3 to 15, evenmore preferably 3 to 10).

It is understood that by having at least one H-donor moiety, thesiloxane-containing vinylic monomer can be more compatible withhydrophilic N-vinyl amide monomer compared to one without any H-donormoiety.

In accordance with the invention, any polysiloxane vinylic crosslinkercan be used in the invention as the first polysiloxane vinyliccrosslinker, so long as it comprises hydrophilized siloxane units eachhaving one methyl substituent and one monovalent 04-040 organic radicalsubstituent having at least teo hydroxyl groups and optional otherH-donor moieties and has a number average molecular weight of from about3000 Daltons to about 80,000 Daltons (preferably from about 4000 toabout 40000 Daltons, more preferably from about 5000 to about 20000Daltons).

While not wishing to be bound by any theory, the inventors believe thatsuch a polysiloxane vinylic crosslinker having hydrophilized siloxaneunits play important roles in having high oxygen permeability and lowmodulus while maintaining the integrity of the contact lens duringhandling. Where a polysiloxane vinylic crosslinker without H-donormoieties or hydrophilic moieties has a number average molecular weighttoo low, the modulus of resultant SiHy lenses would be too high.However, where a polysiloxane vinylic crosslinker without H-donormoieties or hydrophilic moieties has a high number average molecularweight, it is not sufficiently compatible with N-vinyl amide monomer orother hydrophilic polymerizable component and could cause haziness toresultant SiHy contact lenses. With an adequate number of H-donormoieties, a high molecular weight polysiloxane vinylic crosslinker wouldbe sufficiently compatible with N-vinyl amide monomer and otherhydrophilic polymerizable components. In addition, it is believed thatdue to the presence of those H-donor moieties, N-vinyl amide monomermolecules may be preferentially located in the vicinities of such a highmolecular weight polysiloxane vinylic crosslinker because of hydrogenbonding between N-vinyl amide monomer and the H-donor moieties. Duringthe polymerization, in-situ generated poly(N-vinylamide) maypreferentially form inter-penetrating network with hydrophobic siliconeregions and would therefore facilitate the formation of a siliconehydrogel with a macroscopic homogeneity but a microscopic heterogeneity(i.e., microscopic phase separation) for having minimized haziness, highoxygen permeability and high water content.

Preferably, the first polysiloxane vinylic crosslinker comprises: (1) apolysiloxane segment comprising dimethylsiloxane units and hydrophilizedsiloxane units each having one methyl substituent and one monovalentC₄-C₄₀ organic radical substituent having 2 to 6 H-donor moieties,wherein the molar ratio of the hydrophilized siloxane units to thedimethylsiloxane units is from about 0.035 to about 0.15; (2) twoterminal (meth)acryloyl groups; and (3) from 0 to 20 third H-donormoieties, wherein the polysiloxane vinylic crosslinker has a numberaverage molecular weight of from about 3000 Daltons to about 80,000Daltons.

More preferably, the first polysiloxane vinylic crosslinker is acompound of formula (1)

in which:

-   -   ν1 is an integer of from 30 to 500 and ω1 is an integer of from        1 to 75, provided that ω1/ν1 is from about 0.035 to about 0.15        (preferably from about 0.040 to about 0.12, even more preferably        from about 0.045 to about 0.10);    -   X₀₁ is O or NR_(n) in which R_(n) is hydrogen or C₁-C₁₀-alkyl;    -   R_(o) is hydrogen or methyl;    -   R₂ and R₃ independently of each other are a substituted or        unsubstituted C₁-C₁₀ alkylene divalent radical or a divalent        radical of —R₅—O—R₆— in which R₅ and R₆ independently of each        other are a substituted or unsubstituted C₁-C₁₀ alkylene        divalent radical;    -   R₄ is a monovalent radical of any one of formula (2) to (6)

-   -   p1 is zero or 1; m1 is an integer of 2 to 4; m2 is an integer of        1 to 5; m3 is an integer of 3 to 6; m4 is an integer of 2 to 5;    -   R₇ is hydrogen or methyl;    -   R₈ is a C₂-C₆ hydrocarbon radical having (m2+1) valencies;    -   R₉ is a C₂-C₆ hydrocarbon radical having (m4+1) valencies;    -   R₁₀ is ethyl or hydroxymethyl;    -   R₁₁ is methyl or hydromethyl;    -   R₁₂ is hydroxyl or methoxy;    -   X₃ is a sulfur linkage of —S— or a teriary amino linkage of        —NR₁₃— in which R₁₃ is C₁-C₁ alkyl, hydroxyethyl, hydroxypropyl,        or 2,3-dihydroxypropyl; and    -   X₄ is an amide linkage of

in which R₁₄ is hydrogen or C₁-C₁₀ alkyl.

In a preferred embodiment, R₄ is a monovalent radical of one of formula(2a) to (2y).

in which p1 is zero or 1 (preferably 1), m1 is an integer of 2 to 4(preferably 3), R₇ is hydrogen or methyl (preferably hydrogen).

In another preferred embodiment, R₄ a monovalent radical of one offormula (3a) to (3y).

in which X₄ is an amide linkage of

in which R₁₄ is hydrogen or C₁-C₁₀ alkyl.

In another preferred embodiment, R₄ is a monovalent radical of formula(4a) or (4b).

In another preferred embodiment, R₄ a monovalent radical of one offormula (5a) to (5c).

In another preferred embodiment, the monovalent radical R₄ is a radicalof formula (6) in which m1 is 3, p1 is 1, and R₇ is hydrogen. Such apreferred first polysiloxane vinylic crosslinker is represented byformula (A)

in which ν1 and ω1 are as defined above.

A polysiloxane vinylic crosslinker of formula (1) can be prepared byreacting a hydrosiloxane-containing polysiloxane of formula (7) with anene monomer containing 2 to 5 hydroxyl group

in which X₀, R₀, R₂, R₃, ν1, and ω1 are as defined above, in aplatinum-catalyzed hydrosilylation reaction as known to a person skilledin the art.

Hydrosiloxane-containing polysiloxane of formula (7) can be preparedaccording to any methods known to a person skilled in the art. As anillustrative example, a hydrosiloxane-containing polysiloxane of formula(7) can be prepared from polymerization of a mixture ofoctamethylcyclotetrasiloxane (D4) and1,3,5,7-tetramethylcyclotetrasiloxane (H4) in presence of1,3-bis[3-(meth)acryloxypropyl] tetramethyldisiloxane as a chain endblock and in the presence of a catalyst. By controlling the molar ratioof D4 to H4, a desired value of ν1/ω1 can be obtained.

Where in formula (1) R₄ is a monovalent radical of formula (4), (5) or(6), the ene monomer preferred is 3-allyoxy-1,2-propanediol,2-allyloxymethyl-2-(hydroxymethyl)-1,3-propanediol,2-allyloxymethyl-2-ethyl-1,3-propanediol (i.e.,trimethylolpropaneallylether), allyl α-D-mannopyranoside, allylα-D-galactopyranoside, allyl 6-deoxyhexopyranoside, allyl6-deoxy-2-O-methylhexopyranoside, or a fully-hydrolized (i.e.,ring-opening) product of an epoxy-containing ene monomer which isallyloxy glycidyl ether, 1,2-epoxy-5-hexene, 3,4-epoxy-1-butene, or2-methyl-2-vinyloxirane. The above-listed ene monomers are commerciallyavailable.

Where in formula (1) R₄ is a monovalent radical of formula (2), the enemonomer preferred is a reaction product of an epoxy-containing enemonomer with a mercaptan having 2 to 5 hydroxyl groups or a secondaryamine having 2 to 5 hydroxyl groups. Examples of commercially availableepoxy-containing ene monomers include without limitation allyloxyglycidyl ether, 1,2-epoxy-5-hexene, 3,4-epoxy-1-butene, and2-methyl-2-vinyloxirane. Examples of commercially available mercaptanshaving 2 to 4 hydroxyl groups include without limitation1-mercaptoethane-1,2-diol, 2-mercaptopropane-1,3-diol,3-mercaptopropane-1,2-diol, 3-mercaptobutane-1,2-diol,1-mercaptobutane-2,3-diol, 4-mercapto-1,2,3-butanetriol, and2-mercapto-6-methylol-tetrahydropyran-3,4,5-triol. Examples ofcommercially available secondary amines having 2 to 4 hydroxyl groupsinclude without limitation bis(2-hydroxyethyl)amine,bis(2-hydroxypropyl)amine, bis(3-hydroxypropyl)amine,bis-(2,3-dihydroxypropyl)amine, isopropylamino-1,2-propanediol,2-(2-hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol,2-(ethylamino)-1,3-butanediol, 6-ethylamino-1,2,4-cyclohexanetriol,3-(methylamino)-6-methylol-tetrahydropyrantriol,3-(ethylamino)-6-methylol-tetrahydropyrantriol,3-methylamino-1,2-propanediol, 2-methylamino-1,3-propanediol,1-(Methylamino)-1,2,3-propanetriol, 4-methylamino-1,2-butanediol,2-methylamino-1,4-butanediol, 2-methylamino-1,3-butanediol,N-methyl-2,3,4-trihydroxybutylamine,N-methyl-2,3,4,5-tetradroxypentylamine,N-methyl-2,3,4,5,6-pentadroxyhexylamine. Reactions between an epoxideand a mercaptan (to form a thiol ether linakge) and between an epoxideand a secondary amine (to form an amino linakge) are well known to aperson skilled in the art and have been described in the literature.

Where in formula (1) R₄ is a monovalent radical of formula (3), the enemonomer preferred is a reaction product of either (1) acarboxy-containing ene monomer with a primary or secondary amine having2 to 5 hydroxyl groups or (2) a primary amino-containing or secondaryamino-containing ene monomer with an alkanoic acid having 2 to 5hydroxyl groups, according to the well-known coupling reaction betweenone carboxylic acid group and one amino (primary or secondary) group inthe presence of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) andN-hydroxysuccinimide (HO-NHS), to obtain an ene monomer having 2 to 5hydroxyl groups and an amide linkage. Examples of commercially availablecarboxy-containing ene monomers include without limitation 3-butenoicacid, 4-pentenoic acid, 5-hexenoic acid, and 6-heptenoic acid. Examplesof commercially available primary or secondary amino-containing enemonomers include without limitation allylamine, 3-butenylamine,4-pentenylamine, 1-methyl-4-pentenylamine, 5-hexenylamine,5-heptenylamine, 6-heptenylamine, N-ethyl-2-methylallylamine,N-ethylallylamine, N-allylmethylamine, N-allyl-1-pentanamine,N-allyl-2-methyl-1-pentanamine, N-Allyl-2,3-dimethyl-1-pentanamine,N-allyl-1-hexanamine, N-allyl-2-methyl-1-hexanamine, andN-allyl-1-heptanamine. Examples of commercially available alkanoic acidshaving 2 to 5 hydroxyl groups include without limitation2,3-dihydroxy-propanoic acid, 2,3-dihydroxybutanoic acid,3,4-dihydroxybutanoic acid, 2,3,4-trihydroxybutanoic acid,2,4,5-trihydroxypentanoic acid,2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid,3,4,5-trihydroxy-2-methoxypentanoic acid, xylonic acid(2,3,4,5-tetrahydroxypantanoic acid), 3,4,5-trihydroxyhexanoic acid,3,5,6-trihydroxyhexanoic acid, 4,5,6-trihydroxyhexanoic acid,2,4,5,6-tetrahydroxyhexanoic acid, 2,3,4,5-tetrahydroxyhexanoic acid,2,3,4,5,6-pentahydroxyhexanoic acid. Examples of commercially availableprimary amines having 2 to 5 hydroxyl groups include without limitationdihydroxyethylamine, 2,3-dihydropropylamine, 2-amino-1,3-propanediol,2-amino-1,4-butanediol, 2-amino-1,3-butanediol, 4-amino-1,2-butanediol,2-amino-1,3,4-butanetriol, 4-amino-1,2,3-butanetriol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,2-amino-2-(hydroxymethyl)-1,3-propanediol, 2-amino-1,5-pentanediol, and3-amino-6-hydroxymethyl-tetrahydropyran-2,4,5-triol. The above-listedcommercially-available secondary amines having 2 to 5 hydroxyl groupscan be used in the reaction with a carboxy-containing ene monomer toobtain an ene monomer having multiple hydroxyl groups and an amidelinkage. The reaction between a carboxylic acid group and a primary orsecondary amino group to form an amide linkage is well known to a personskilled in the art and has been described extensively in the literature.

The procedures for preparing a polysiloxane vinylic crosslinkers offormula (1) have also been described in detail in U.S. Pat. Appl. Pub.No. 2017-0166673 A1.

It is understood that the fourth repeating units of at least one secondpolysiloxane vinylic crosslinkers are optional components. Any suitablepolysiloxane vinylic crosslinkers other than those polysiloxane vinyliccrosslinkers having hydrophilized siloxane units described above can beused in the inventions, so long as each of them comprises at least onepolysiloxane segment and at least two ethylenically unsaturated groups.Examples of such polysiloxane vinylic crosslinkers aredi-(meth)acryloyloxy-terminated polydimethylsiloxanes of variousmolecular weight; divinyl carbonate-terminated polydimethylsiloxanes;divinyl carbamate-terminated polydimethylsiloxane; divinyl terminatedpolydimethylsiloxanes of various molecular weight;di-(meth)acrylamido-terminated polydimethylsiloxanes; N, N, N′,N′-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane;chain-extended polysiloxane vinylic crosslinkers which comprises atleast two polysiloxane segments and at least one divalent organicradical linking each pair of adjacent polysiloxane segments and havingone or more H-donor moieties (see, e.g., those disclosed in U.S. Pat.Nos. 5,034,461, 5,416,132, 5,449,729, 5,760,100, 7,423,074, 8,529,057,and 8,993,651 and in U.S. Pat. App. Pub. No. 2018-0100053 A1);siloxane-containing macromer selected from the group consisting ofMacromer A, Macromer B, Macromer C, and Macromer D described in U.S.Pat. No. 5,760,100; the reaction products of glycidyl methacrylate withamino-functional polydimethylsiloxanes; polysiloxane-containingmacromers disclosed in U.S. Pat. Nos. 4,136,250, 4,153,641, 4,182,822,4,189,546, 4,343,927, 4,254,248, 4,355,147, 4,276,402, 4,327,203,4,341,889, 4,486,577, 4,543,398, 4,605,712, 4,661,575, 4,684,538,4,703,097, 4,833,218, 4,837,289, 4,954,586, 4,954,587, 5,010,141,5,034,461, 5,070,170, 5,079,319, 5,039,761, 5,346,946, 5,358,995,5,387,632, 5,416,132, 5,451,617, 5,486,579, 5,962,548, 5,981,675,6,039,913, and 6,762,264; polysiloxane-containing macromers disclosed inU.S. Pat. Nos. 4,259,467, 4,260,725, and 4,261,875.

Examples of preferred di-(meth)acryloyl-terminated polydiorganosiloxanesinclude without limitation α,ω-bis[3-(meth)acrylamidopropyl]-terminatedpolydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxy-isopropyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[(meth)acrylamidoethylamino-2-hydroxypropyloxy-propyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamidopropylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[3-(meth)acrylamide-butylamino-2-hydroxypropyloxypropyl]-terminatedpolydimethylsiloxane, a,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminatedpolydimethylsiloxane,α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane,α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-(polyethylenoxy)propyl]-terminatedpolydimethylsiloxane,α,ω-bis[(meth)acryloxyethylamino-carbonyloxy-ethoxypropyl]-terminatedpolydimethylsiloxane,α,ω-bis[(meth)acryloxyethylamino-carbonyloxy-(polyethylenoxy)propyl]-terminatedpolydimethylsiloxane.

In accordance with the invention, any suitable N-vinyl amide monomerscan be used in the invention. Examples of preferred N-vinyl amidemonomers include without limitation N-vinyl pyrrolidone, N-vinylpiperidone, N-vinyl caprolactam, N-vinyl-N-methyl acetamide, N-vinylformamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, andmixtures thereof. Preferably, the N-vinyl amide monomer isN-vinylpyrrolidone, N-vinyl-N-methyl acetamide, or combinations thereof.

In accordance with the invention, a silicone hydrogel contact lens ofthe invention can further comprise (but preferably comprises) repeatingunits of one or more non-silicone vinylic crosslinking agents,preferably in an amount of about 1.0% or less (preferably about 0.8% orless, more preferably from about 0.05% to about 0.6%) by weight relativeto the dry weight of the silicone hydrogel contact lens. The amount ofthe repeating units of a non-silicone vinylic crosslinking agent can becalculated based on the amount of the non-silicone vinylic crosslinkingagent in a polymerizable composition used for preparing the siliconehydrogel contact lens over the total amount of all polymerizablecomponents in the polymerizable composition.

Examples of preferred non-silicone vinylic cross-linking agents includewithout limitation ethyleneglycol di-(meth)acrylate, diethyleneglycoldi-(meth)acrylate, triethyleneglycol di-(meth)acrylate,tetraethyleneglycol di-(meth)acrylate, glycerol di-(meth)acrylate,1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate,1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerolatedi-(meth)acrylate, ethylenebis[oxy(2-hydroxypropane-1,3-diyl)]di-(meth)acrylate, bis[2-(meth)acryloxyethyl] phosphate,trimethylolpropane di-(meth)acrylate, and3,4-bis[(meth)acryloyl]tetrahydrofuan, diacrylamide, dimethacrylamide,N, N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine,N,N′-methylene bis(meth)acrylamide, N,N′-ethylene bis(meth)acrylamide,N,N′-dihydroxyethylene bis(meth)acrylamide, N,N′-propylenebis(meth)acrylamide, N,N′-2-hydroxypropylene bis(meth)acrylamide,N,N′-2,3-dihydroxybutylene bis(meth)acrylamide,1,3-bis(meth)acrylamidepropane-2-yl dihydrogen phosphate (i.e.,N,N′-2-phosphonyloxypropylene bis(meth)acrylamide), piperazinediacrylamide (or 1,4-bis(meth)acryloyl piperazine), tetraethyleneglycoldivinyl ether, triethyleneglycol divinyl ether, diethyleneglycol divinylether, ethyleneglycol divinyl ether, triallyl isocyanurate, triallylcyanurate, trimethylopropane trimethacrylate, pentaerythritoltetramethacrylate, bisphenol A dimethacrylate, and combinations thereof.A preferred non-silicone vinylic cross-linking agent istetra(ethyleneglycol) di-(meth)acrylate, tri(ethyleneglycol)di-(meth)acrylate, ethyleneglycol di-(meth)acrylate, di(ethyleneglycol)di-(meth)acrylate, tetraethyleneglycol divinyl ether, triethyleneglycoldivinyl ether, diethyleneglycol divinyl ether, ethyleneglycol divinylether, triallyl isocyanurate, or triallyl cyanurate.

In accordance with the invention, a silicone hydrogel contact lens ofthe invention preferably can further comprise repeating units of one ormore blending vinylic monomers, preferably in an amount of about 25% orless by weight (preferably about 20% or less by weight, more preferablyabout 15% or less by weight, relative to the dry weight of the siliconehydrogel contact lens. The amount of the repeating units of a blendingvinylic monomer can be calculated based on the amount of the blendingvinylic monomer in a polymerizable composition used for preparing thesilicone hydrogel contact lens over the total amount of allpolymerizable components in the polymerizable composition.

Examples of preferred blending vinylic monomers include C₁-C₁₀ alkyl(meth)acrylate (e.g., methyl (meth)acrylate, ethyl (meth)acrylate,propyl (meth)acrylate, isopropyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, etc.),cyclopentylacrylate, cyclohexylmethacrylate, cyclohexylacrylate,isobornyl (meth)acrylate, styrene, 4,6-trimethylstyrene (TMS), t-butylstyrene (TBS), trifluoroethyl (meth)acrylate, hexafluoro-isopropyl(meth)acrylate, hexafluorobutyl (meth)acrylate, or combinations thereof.Preferably, methyl methacrylate is used as a blending vinylic monomer.

In accordance with a preferred embodiment of the invention, a siliconehydrogel contact lens of the invention can further comprise (butpreferably comprises) repeating units of one or more UV-absorbingvinylic monomers and optionally (but preferably) one or moreUV/HEVL-absorbing vinylic monomers. The term “UV/HEVL-absorbing vinylicmonomer” refers to a vinylic monomer that can absorb UV light andhigh-energy-violet-light (i.e., light having wavelength between 380 nmand 440 nm.

Any suitable UV-absorbing vinylic monomers and UV/HEVL-absorbing vinylicmonomers can be used in a polymerizable composition for preparing apolymer of the invention. Examples of preferred UV-absorbing andUV/HEVL-absorbing vinylic monomers include without limitation:2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole,2-(2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl) benzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-methoxybenzotriazole,2-(2′-hydroxy-5′-methacryloxypropyl-3′-t-butyl-phenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacryloxypropyl phenyl) benzotriazole,2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-1),2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-5),3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate (WL-2),3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate (WL-3),3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate (WL-4),2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-6),2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-7),4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol(WL-8),2-{2′-Hydroxy-3′-tert-5-[3″-(4″-vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole,phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-ethenyl-(UVAM), 2-[2′-hydroxy-5′-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole(2-Propenoic acid, 2-methyl-,2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl ester, Norbloc),2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole(UV13),2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole(UV28),2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole(UV23), 2-(2′-hydroxy-5-methacrylamidophenyl)-5-methoxybenzotriazole(UV6), 2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV9),2-(2-Hydroxy-3-methallyl-5-methylphenyl)-2H-benzotriazole (UV12),2-3′-t-butyl-2′-hydroxy-5′-(3″-dimethylvinylsilylpropoxy)-2′-hydroxy-phenyl)-5-methoxybenzotriazole(UV15),2-(2′-hydroxy-5′-methacryloylpropyl-3′-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole(UV16),2-(2′-hydroxy-5′-acryloylpropyl-3′-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole(UV16A), 2-Methylacrylic acid3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propylester (16-100, CAS #96478-15-8),2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethylmethacrylate (16-102); Phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl) (CAS#1260141-20-5);2-[2-Hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazole;Phenol, 2-(5-ethenyl-2H-benzotriazol-2-yl)-4-methyl-, homopolymer (901)(CAS #83063-87-0). In accordance with the invention, the polymerizablecomposition comprises about 0.1% to about 3.0%, preferably about 0.2% toabout 2.5%, more preferably about 0.3% to about 2.0%, by weight of oneor more UV-absorbing vinylic monomers, related to the amount of allpolymerizable components in the polymerizable composition.

In a preferred embodiment, a silicone hydrogel contact lens of theinvention comprises repeating units of a UV-absorbing vinylic monomerand repeating units of a UV/HEVL absorbing vinylic monomer. Morepreferably, the silicone hydrogel contact lens is characterized byhaving the UVB transmittance of about 10% or less (preferably about 5%or less, more preferably about 2.5% or less, even more preferably about1% or less) between 280 and 315 nanometers and a UVA transmittance ofabout 30% or less (preferably about 20% or less, more preferably about10% or less, even more preferably about 5% or less) between 315 and 380nanometers and and a Violet transmittance of about 70% or less,preferably about 60% or less, more preferably about 50% or less, evenmore preferably about 40% or less) between 380 nm and 440 nm. Even morepreferably, the UV-absorbing vinylic monomer is2-[2′-hydroxy-5′-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole(Norbloc), and the UV/HEVL absorbing vinylic monomer is2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole(UV13),2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole(UV28),2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole(UV23), or combinations thereof.

In accordance with the invention, a silicone hydrogel contact lens ofthe invention can further comprise repeating units of one or morehydrophilic acrylic monomers, preferably in an amount of about 10% orless (preferably about 8% or less, more preferably about 5% or less) byweight relative to the dried weight of the silicone hydrogel contactlens. The amount of the repeating units of a hydrophilic acrylic monomercan be calculated based on the amount of the hydrophilic acrylic monomerin a polymerizable composition used for preparing the silicone hydrogelcontact lens over the total amount of all polymerizable components inthe polymerizable composition.

Examples of preferred hydrophilic acrylic monomers include withoutlimitation N,N-dimethyl (meth)acrylamide, (meth)acrylamide,N-hydroxylethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide,hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), polyethyleneglycol (meth)acrylate having a number average molecular weight of up to1500, polyethylene glycol C₁-C₄-alkyl ether (meth)acrylate having anumber average molecular weight of up to 1500,N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid,ethylacrylic acid, and combinations thereof. Preferably, the hydrophilicvinylic monomer is N,N-dimethyl (meth)acrylamide, hydroxyethyl(meth)acrylate, N-hydroxylethyl (meth)acrylamide, glycerol methacrylate(GMA), or combinations thereof.

A silicone hydrogel contact lens of the invention can also compriseother necessary components known to a person skilled in the art, suchas, for example, one or more free radical initiator, a visibilitytinting agent (e.g., repeating units of one or more polymerizable dyes,pigments, or mixtures thereof), antimicrobial agents (e.g., preferablysilver nanoparticles), a bioactive agent, leachable lubricants,leachable tear-stabilizing agents, and mixtures thereof, as known to aperson skilled in the art.

Suitable thermal polymerization initiators are known to the skilledartisan and comprise, for example peroxides, hydroperoxides,azo-bis(alkyl- or cycloalkylnitriles), persulfates, percarbonates ormixtures thereof. Examples are benzoylperoxide, tert.-butyl peroxide,di-tert.-butyl-diperoxyphthalate, tert.-butyl hydroperoxide,azo-bis(isobutyronitrile) (AIBN), 1,1-azodiisobutyramidine, 1,1′-azo-bis(1-cyclohexanecarbonitrile), 2,2′-azo-bis(2,4-dimethyl-valeronitrile)and the like.

Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone,a benzoylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and Darocurand Irgacur types, preferably Darocur 1173® and Darocur 2959®,Germane-based Norrish Type I photoinitiators. Examples ofbenzoylphosphine initiators include2,4,6-trimethylbenzoyldiphenylophosphine oxide;bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; andbis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. Reactivephotoinitiators, which can be incorporated, for example, into a macromeror can be used as a special monomer, are also suitable. Examples ofreactive photoinitiators are those disclosed in EP 632 329.

Where a vinylic monomer capable of absorbing ultra-violet radiation andhigh energy violet light (HEVL) is used in the invention, aGermane-based Norrish Type I photoinitiator and a light source includinga light in the region of about 400 to about 550 nm are preferably usedto initiate a free-radical polymerization. Any Germane-based NorrishType I photoinitiators can be used in this invention, so long as theyare capable of initiating a free-radical polymerization underirradiation with a light source including a light in the region of about400 to about 550 nm. Examples of Germane-based Norrish Type Iphotoinitiators are acylgermanium compounds described in U.S. Pat. No.7,605,190.

The bioactive agent is any compound that can prevent a malady in the eyeor reduce the symptoms of an eye malady. The bioactive agent can be adrug, an amino acid (e.g., taurine, glycine, etc.), a polypeptide, aprotein, a nucleic acid, or any combination thereof. Examples of drugsuseful herein include, but are not limited to, rebamipide, ketotifen,olaptidine, cromoglycolate, cyclosporine, nedocromil, levocabastine,lodoxamide, ketotifen, or the pharmaceutically acceptable salt or esterthereof. Other examples of bioactive agents include2-pyrrolidone-5-carboxylic acid (PCA), alpha hydroxyl acids (e.g.,glycolic, lactic, malic, tartaric, mandelic and citric acids and saltsthereof, etc.), linoleic and gamma linoleic acids, and vitamins (e.g.,B5, A, B6, etc.).

Examples of leachable lubricants include without limitation mucin-likematerials (e.g., polyglycolic acid) and non-crosslinkable hydrophilicpolymers (i.e., without ethylenically unsaturated groups). Anyhydrophilic polymers or copolymers without any ethylenically unsaturatedgroups can be used as leachable lubricants. Preferred examples ofnon-crosslinkable hydrophilic polymers include, but are not limited to,polyvinyl alcohols (PVAs), polyamides, polyimides, polylactone, ahomopolymer of a vinyl lactam, a copolymer of at least one vinyl lactamin the presence or in the absence of one or more hydrophilic vinyliccomonomers, a homopolymer of acrylamide or methacrylamide, a copolymerof acrylamide or methacrylamide with one or more hydrophilic vinylicmonomers, polyethylene oxide (i.e., polyethylene glycol (PEG)), apolyoxyethylene derivative, poly-N—N-dimethylacrylamide, polyacrylicacid, poly 2 ethyl oxazoline, heparin polysaccharides, polysaccharides,and mixtures thereof. The number average molecular weight M_(w) of thenon-crosslinkable hydrophilic polymer is preferably from 5,000 to1,000,000.

Examples of leachable tear-stabilizing agents include, withoutlimitation, phospholipids, monoglycerides, diglycerides, triglycerides,glycolipids, glyceroglycolipids, sphingolipids, sphingo-glycolipids,fatty alcohols, fatty acids, mineral oils, and mixtures thereof.Preferably, a tear stabilizing agent is a phospholipid, a monoglyceride,a diglyceride, a triglyceride, a glycolipid, a glyceroglycolipid, asphingolipid, a sphingo-glycolipid, a fatty acid having 8 to 36 carbonatoms, a fatty alcohol having 8 to 36 carbon atoms, or a mixturethereof.

In a preferred embodiment, a silicone hydrogel contact lens of theinvention comprises about 60% or more by weight (preferably about 65% ormore by weight, more preferably about 70% or more by weight, even morepreferably about 75% or more by weight) of the first, second, and thirdrepeating units relative to the dry weight of the silicone hydrogelcontact lens. The total amount of the first, second, and third repeatingunits can be calculated based on the sum of the amounts of thesiloxane-containing vinylic monomer, the first polysiloxane vinyliccrosslinker and the hydrophilic N-vinyl amide monomer in a polymerizablecomposition used for preparing the silicone hydrogel contact lens overthe total amount of all polymerizable components in the polymerizablecomposition.

A silicone hydrogel contact lens of the invention can be prepared from apolymerizable composition (i.e., a lens-forming composition or a lensformulation) according to a method of the invention which is anotheraspect of the invention.

A polymerizable composition can be prepared by dissolving all of thedesirable components in any suitable solvent, such as, a mixture ofwater and one or more organic solvents miscible with water, an organicsolvent, or a mixture of one or more organic solvents, as known to aperson skilled in the art. The term “solvent” refers to a chemical thatcannot participate in free-radical polymerization reaction.

Example of preferred organic solvents includes without limitation,tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycolmethyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone,methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethyleneglycol methyl ether, ethylene glycol phenyl ether, propylene glycolmethyl ether, propylene glycol methyl ether acetate, dipropylene glycolmethyl ether acetate, propylene glycol n-propyl ether, dipropyleneglycol n-propyl ether, tripropylene glycol n-butyl ether, propyleneglycol n-butyl ether, dipropylene glycol n-butyl ether, tripropyleneglycol n-butyl ether, propylene glycol phenyl ether dipropylene glycoldimethyl ether, polyethylene glycols, polypropylene glycols, ethylacetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate,i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol,menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol,3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol,2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol,tert-amyl alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol,3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol,3,7-dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol,2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonanol,2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol,4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol,3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol,3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol,4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol,1-methylcyclopentanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol,3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol,2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol,2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol,1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, isopropanol,1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethyl formamide,dimethyl acetamide, dimethyl propionamide, N-methyl pyrrolidinone, andmixtures thereof.

In another aspect, the present invention provides a method for producinginherently-wettable silicone hydrogel contact lenses. The methodcomprises the steps of: preparing a polymerizable composition which isclear at room temperature and optionally but preferably at a temperatureof from about 0 to about 4° C., wherein the polymerizable compositioncomprises (a) at least one siloxane-containing vinylic monomer including0 to 10 first H-donor moieties, (b) at least one first polysiloxanevinylic crosslinker which has (iv) a number average molecular weight offrom about 3000 Daltons to about 80,000 Daltons and comprises (i) twoterminal (meth)acryloyl groups, (ii) at least one polysiloxane segmentcomprising dimethylsiloxane units and hydrophilized siloxane units eachhaving one methyl substituent and one monovalent C₄-C₄₀ organic radicalsubstituent having one or more second H-donor moieties, and (iii) from 0to 20 third H-donor moieties which are integral parts of molecularstructures outside of the polysiloxane segment, (c) at least onehydrophilic N-vinyl amide monomer, (d) optionally at least one secondpolysiloxane vinylic crosslinker having 0 to 35 fourth H-donor moieties,and (e) at least one free radical initiator, wherein the first andsecond polysiloxane vinylic crosslinker are different from each other,wherein the first, second, third and fourth H-donor moieties independentof one another are hydroxyl groups, carboxyl groups, amino groups of—NHR^(o), amino linkages of —NH—, amide linkages of —CONH—, urethanelinkages of —OCONH—, or combinations thereof, wherein R^(o) is H or aC₁-C₄ alkyl, wherein the polymerizable composition comprises at least8.8 (preferably at least 9.0, more preferably at least 9.2, even morepreferably at least 9.6) mmoles of component (c) per gram of allcomponents (a), (b) and (d) in in total and at least 0.11 (preferably atleast 0.15, more preferably at least 0.20, even more preferably at least0.25) meqs of the first, second, third and fourth H-donor moieties intotal per gram of component (c); introducing the polymerizablecomposition into a lens mold; curing thermally or actinically thepolymerizable composition in the lens mold to form a silicone hydrogelcontact lens, wherein the silicone hydrogel contact lens has an oxygenpermeability of at least 50 barrers, an elastic modulus of from about0.2 MPa to about 1.5 MPa, and an equilibrium water content of from about40% to about 70% and is inherently wettable as characterized by having awater-break-up-time of at least 10 seconds and a water contact angle bycaptive bubble of about 80 degrees or less without being subjected toany post-curing surface treatment.

Various embodiments described above of siloxane-containing vinylicmonomers, polysiloxane vinylic crosslinkers, hydrophilic N-vinyl amidemonomers, non-silicone vinylic crosslinking agents, blending vinylicmonomers, UV-absorbing vinylic monomers, hydrophilic vinylic monomers,free radical initiators, visibility-tinting agents, and solvents shouldbe incorporated into this aspect of the invention.

In a preferred embodiment, a polymerizable composition of the inventioncomprises about 60% or more by weight (preferably about 65% or more byweight, more preferably about 70% or more by weight, even morepreferably about 75% or more by weight) of all components (a), (b) and(c) in total relative to the total weight of all polymerizablecomponents in the polymerizable composition.

The thermal polymerization is carried out conveniently in anabove-mentioned solvent at elevated temperature, for example at atemperature of from 25 to 100° C. and preferably 40 to 80° C. Thereaction time may vary within wide limits, but is conveniently, forexample, from 1 to 24 hours or preferably from 2 to 12 hours. It isadvantageous to previously degas the components and solvents used in thepolymerization reaction and to carry out said copolymerization reactionunder an inert atmosphere, for example under a nitrogen or argonatmosphere.

The actinic polymerization can then be triggered off by actinicradiation, for example light, in particular UV light or visible light ofa suitable wavelength. The spectral requirements can be controlledaccordingly, if appropriate, by addition of suitable photosensitizers.

Lens molds for making contact lenses are well known to a person skilledin the art and, for example, are employed in cast molding or spincasting. For example, a mold (for cast molding) generally comprises atleast two mold sections (or portions) or mold halves, i.e. first andsecond mold halves. The first mold half defines a first molding (oroptical) surface and the second mold half defines a second molding (oroptical) surface. The first and second mold halves are configured toreceive each other such that a lens forming cavity is formed between thefirst molding surface and the second molding surface. The moldingsurface of a mold half is the cavity-forming surface of the mold and indirect contact with lens-forming material.

Methods of manufacturing mold sections for cast-molding a contact lensare generally well known to those of ordinary skill in the art. Theprocess of the present invention is not limited to any particular methodof forming a mold. In fact, any method of forming a mold can be used inthe present invention. The first and second mold halves can be formedthrough various techniques, such as injection molding or lathing.Examples of suitable processes for forming the mold halves are disclosedin U.S. Pat. Nos. 4,444,711; 4,460,534; 5,843,346; and 5,894,002.

Virtually all materials known in the art for making molds can be used tomake molds for making contact lenses. For example, polymeric materials,such as polyethylene, polypropylene, polystyrene, PMMA, Topas® COC grade8007-S10 (clear amorphous copolymer of ethylene and norbornene, fromTicona GmbH of Frankfurt, Germany and Summit, N.J.), or the like can beused. Other materials that allow UV light transmission could be used,such as quartz glass and sapphire.

In accordance with the invention, the polymerizable composition can beintroduced (dispensed) into a cavity formed by a mold according to anyknown methods.

After the polymerizable composition is dispensed into the mold, it ispolymerized to produce a contact lens. Crosslinking may be initiatedthermally or actinically to crosslink the polymerizable components inthe polymerizable composition.

Opening of the mold so that the molded article can be removed from themold may take place in a manner known per se.

The molded contact lens can be subject to lens extraction to removeunpolymerized polymerizable components. The extraction solvent can beany solvent known to a person skilled in the art. Examples of suitableextraction solvent are those solvent described above. After extraction,lenses can be hydrated in water or an aqueous solution of a wettingagent (e.g., a hydrophilic polymer).

The molded contact lenses can further subject to further processes, suchas, for example, hydration, packaging in lens packages with a packagingsolution which is well known to a person skilled in the art;sterilization such as autoclave at from 118 to 124° C. for at leastabout 30 minutes; and the like.

Lens packages (or containers) are well known to a person skilled in theart for autoclaving and storing a soft contact lens. Any lens packagescan be used in the invention. Preferably, a lens package is a blisterpackage which comprises a base and a cover, wherein the cover isdetachably sealed to the base, wherein the base includes a cavity forreceiving a sterile packaging solution and the contact lens.

Lenses are packaged in individual packages, sealed, and sterilized(e.g., by autoclave at about 120° C. or higher for at least 30 minutesunder pressure) prior to dispensing to users. A person skilled in theart will understand well how to seal and sterilize lens packages.

In accordance with the invention, a packaging solution contains at leastone buffering agent and one or more other ingredients known to a personskilled in the art. Examples of other ingredients include withoutlimitation, tonicity agents, surfactants, antibacterial agents,preservatives, and lubricants (e.g., cellulose derivatives, polyvinylalcohol, polyvinyl pyrrolidone).

Although various embodiments of the invention have been described usingspecific terms, devices, and methods, such description is forillustrative purposes only. The words used are words of descriptionrather than of limitation. As would be obvious to one skilled in theart, many variations and modifications of the invention may be made bythose skilled in the art without departing from the spirit and scope ofthe novel concepts of the disclosure. In addition, it should beunderstood that aspects of the various embodiments of the invention maybe interchanged either in whole or in part or can be combined in anymanner and/or used together.

The previous disclosure will enable one having ordinary skill in the artto practice the invention. Various modifications, variations, andcombinations can be made to the various embodiment described herein. Inorder to better enable the reader to understand specific embodiments andthe advantages thereof, reference to the following examples issuggested. It is intended that the specification and examples beconsidered as exemplary.

Example 1

Oxygen Permeability Measurements

Unless specified, the apparent oxygen permeability (Dk_(app)), theapparent oxygen transmissibility (Dk/t), the intrinsic (oredge-corrected) oxygen permeability (Dk_(i) or Dk_(c)) of a lens and alens material are determined according to procedures described inExample 1 of U.S. Pat. Appl. Pub. No. 2012-0026457 A1.

Surface Wettability Tests

Water contact angle (WCA) on a contact lens is a general measure of thesurface wettability of a contact lens. In particular, a low watercontact angle corresponds to more wettable surface. The dynamic captivebubble contact angles of contact lenses are measured using a FDSinstrument device from FDS Future Digital Scientific Corp. The FDSequipment is capable of measuring the advancing and receding contactangles. The measurement is performed on hydrated contact lenses at roomtemperature. A contact lens is removed from the vial and soaked in ˜40mL fresh phosphate buffered saline (PBS) and shake for at least 30minutes, then replace with fresh PBS, soak and shake for another 30minutes unless otherwise specified. The contact lens is then put on alens paper and dabbed to remove surface water prior to be placed on topof a lens holder with front curve up then screw the lens holder top on.Place the secure lens holder into the glass cell cuvette filled withfiltered PBS. Place the glass cell cuvette onto the stage of the FDSinstrument. Adjust the stage height and the syringe needle to dispensethe air bubble to the lens surface. Repeat dispense/withdrawl 3 cyclesfor every lens to get the advancing and receding contact angles. Thereceding contact angles are reported in the examples below.

Water Break-Up Time (WBUT) Tests

The surface hydrophilicity of lenses (after autoclave) is assessed bydetermining the time required for the water film to start breaking onthe lens surface. Lenses exhibiting WBUT 10 seconds are considered tohave a hydrophilic surface and are expected to exhibit adequatewettability (ability to support the tear film) on-eye.

Lenses are prepared for water breakup measurement by removing the lensfrom its blister with soft plastic tweezers (Menicon) and placing thelens in a beaker containing phosphate buffered saline. The beakercontains at least 20 mL phosphate buffered saline per lens, with up to 3lenses per beaker. Lenses are soaked for a minimum 30 minutes up to 24hours before being transferred with soft plastic tweezers into a 96 wellplastic tray with fresh phosphate buffered saline.

Water breakup time is measured at room temperature as follows: lensesare picked up with soft plastic tweezers as close to the edge of thelens as possible, base curve toward the measurer, taking care that thelens does not touch the sides of the well after being removed from thesaline. As illustrated schematically in FIG. 1, the lens (101) is shakenonce to remove excess saline and a timer is started. Ideally, the waterfilm (120) in the base curve surface of the lens will recede from thepoint of contact with the tweezers's tips (111) in a uniform, circularpattern (125). When approximately 30% of the hydrated area (125) hasreceded, the timer is stopped and this time is recorded as the waterbreakup time (WBUT). Lenses that do not display the ideal recedingpattern can be placed back in the tray and re-measured, afterrehydrating for at least 30 seconds.

Equilibrium Water Content

The equilibrium water content (EWC) of contact lenses are determined asfollows.

Amount of water (expressed as percent by weight) present in a hydratedhydrogel contact lens, which is fully equilibrated in saline solution,is determined at room temperature. Quickly stack the lenses, andtransfer the lens stack to the aluminum pan on the analytical balanceafter blotting lens in a cloth. The number of lenses for each sample panis typically five (5). Record the pan plus hydrated weight of thelenses. Cover the pan with aluminum foil. Place pans in a laboratoryoven at 100±2° C. to dry for 16-18 hours. Remove pan plus lenses fromthe oven and cool in a desiccator for at least 30 minutes. Remove asingle pan from the desiccator, and discard the aluminum foil. Weigh thepan plus dried lens sample on an analytical balance. Repeat for allpans. The wet and dry weight of the lens samples can be calculated bysubtracting the weight of the empty weigh pan.

Elastic Modulus

The elastic modulus of a contact lens is determined using a MTS insightinstrument. The contact lens is first cut into a 3.12 mm wide stripusing Precision Concept two stage cutter. Five thickness values aremeasured within 6.5 mm gauge length. The strip is mounted on theinstrument grips and submerged in PBS (phosphate buffered saline) withthe temperature controlled at 21±2° C. Typically 5N Load cell is usedfor the test. Constant force and speed is applied to the sample untilthe sample breaks. Force and displacement data are collected by theTestWorks software. The elastic modulus value is calculated by theTestWorks software which is the slope or tangent of the stress vs.strain curve near zero elongation, in the elastic deformation region.

Transmittance

Contact lenses are manually placed into a specially fabricated sampleholder or the like which can maintain the shape of the lens as it wouldbe when placing onto eye. This holder is then submerged into a 1 cmpath-length quartz cell containing phosphate buffered saline (PBS, pH˜7.0-7.4) as the reference. A UV/visible spectrpohotmeter, such as,Varian Cary 3E UV-Visible Spectrophotometer with a LabSphere DRA-CA-302beam splitter or the like, can be used in this measurement. Percenttransmission spectra are collected at a wavelength range of 250-800 nmwith % T values collected at 0.5 nm intervals. This data is transposedonto an Excel spreadsheet and used to determine if the lenses conform toClass 1 UV absorbance. Transmittance is calculated using the followingequations:

${{UVA}\mspace{14mu}\% T} = {\frac{{Average}\mspace{14mu}\%\mspace{14mu} T\mspace{14mu}{between}\mspace{14mu} 380\text{-}316\mspace{11mu}{nm}}{{Luminescence}\mspace{14mu}\% T} \times 100}$${{UVB}\mspace{14mu}\% T} = {\frac{{Average}\mspace{14mu}\%\mspace{14mu} T\mspace{14mu}{between}\mspace{14mu} 280\text{-}315\mspace{11mu}{nm}}{{Luminescence}\mspace{14mu}\% T} \times 100}$${{Violet}\mspace{14mu}\% T} = {\frac{{Average}\mspace{14mu}\%\mspace{14mu} T\mspace{14mu}{between}\mspace{14mu} 440\text{-}380\mspace{11mu}{nm}}{{Luminescence}\mspace{14mu}\% T} \times 100}$in which Luminescence % T is the average % transmission between 380 and780.Chemicals

The following abbreviations are used in the following examples: NVPrepresents N-vinylpyrrolidone; DMA represents N,N-dimethylacrylamide;VMA represents N-vinyl-N-methyl acetamide; MMA represents methylmethacrylate; TEGDMA represent triethyleneglycol dimethacrylate; TEGDVErepresents triethyleneglycol divinyl ether; EGMA represents ethyleneglycol methyl ether methacrylate; VAZO 64 represents2,2′-dimethyl-2,2′azodipropiononitrile; Nobloc is2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate fromAldrich; UV28 represents2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole;RB246 is Reactive Blue 246; RB247 is Reactive Blue 247; TAA representstert-amyl alcohol; PrOH represents 1-propanol; IPA representsisopropanol; DC 1173 represents Darocur 1173® photoinitiator; MeCNrepresents acetonitrile; SiGMA represents3-(3-methacryloxy-2-hydroxypropyloxypropyl-bis(trimethylsiloxy)methylsilane;mSi1 represents monobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜600 to 800 g/mol from Gelest); mSi2 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜1100 g/mol from Gelest); D3 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜539 g/mol from Shin-Etsu); D6 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜761 g/mol from Shin-Etsu); D9 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜984 g/mol from Shin-Etsu); D7 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜750 g/mol from Shin-Etsu); D8 representsmonobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (Mw˜850 g/mol from Shin-Etsu); LM-CEPDMS representsa di-methacrylate-terminated chain-extended polydimethylsiloxane(Mn˜6000 g/mol), which has three polydimethylsiloxane (PDMS) segmentslinked via diurethane linkages between two PDMS segments and twourethane linkages each located between one terminal methacrylate groupand one PDMS segment, is prepared according to a method similar to whatdescribed in Example 2 of U.S. Pat. No. 8,529,057; CEPDMS represents adi-methacrylate-terminated chain-extended polydimethylsiloxane (Mn˜9000g/mol), which has three polydimethylsiloxane (PDMS) segments linked viadiurethane linkages between two PDMS segments and two urethane linkageseach located between one terminal methacrylate group and one PDMSsegment, is prepared according to method similar to what described inExample 2 of U.S. Pat. No. 8,529,057; Betacon represents adimethacrylate-terminated chain-extended polydimethylsiloxane (Mn˜5000g/mol), which has two polydimethylsiloxane (PDMS) segments separated byone perfluoropolyether (PFPE) via diurethane linkages between PDMS andPFPE segments and two urethane linkages each located between oneterminal methacrylate group and one PDMS segment, is prepared accordingto method similar to what described in Example B-1 of U.S. Pat. No.5,760,100; “GA” macromer represents adi-methacryloyloxypropyl-terminated polysiloxane (Mn˜6.8K g/mol, OHcontent˜1.2 meq/g) of formula (A) shown above; “G0” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜8.0K g/mol, OHcontent 1.8 meq/g) of formula (A) shown above; “G1” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜10.7K g/mol, OHcontent˜1.8 meq/g) of formula (A) shown above; “G3” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜16.3K g/mol, OHcontent˜1.8 meq/g) of formula (A) shown above; “G4” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜13.5K g/mol, OHcontent 1.8 meq/g) of formula (A) shown above; “G5” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜14.8K g/mol, OHcontent˜2.2 meq/g) of formula (A) shown above; “G6” macromer representsa di-methacryloyloxypropyl-terminated polysiloxane (Mn˜17.9K g/mol, OHcontent˜2.2 meq/g) of formula (A) shown above. All thedi-methacryloyloxypropyl-terminated polysiloxane of formula (A) areprepared according to the procedures described in U.S. Pat. Appl. Pub.No. 2017-0166673 A1.

Example 2

A lens formulation is purged with nitrogen at room temperature for 30 to35 minutes. The N₂-purged lens formulation is introduced intopolypropylene molds and thermally cured in an oven under the followingcuring conditions: ramping from room temperature to a first temperatureand then holding at the first temperature for a first curing timeperiod; ramping from the first temperature to a second temperature andholding at the second temperature for a second curing time period;optionally ramping from the second temperature to a third temperatureand holding at the third temperature for a third curing time period; andoptionally ramping from the third temperature to a fourth temperatureand holding at the fourth temperature for a fourth curing time period.

Lens molds are opened by using a demolding machine with a push pin.Lenses are pushed onto base curve molds with a push pin and then moldsare separated into base curve mold halves and front curve mold halves.The base curve mold halves with a lens thereon are placed in anultrasonic device (e.g., Dukane's single horn ultrasonic device). With acertain energy force, a dry state lens is relased from mold. The drystate lens is loaded in a designed extraction tray. Alternatively,lenses can be removed from the base curve mold halves by floating off(i.e., soaking in an organic solvent, e.g., IPA, without ultrasonic).The lenses removed from the molds are subjected to an extraction processusing water or an organic solvent or a mixture of solvents for at least30 minutes. For example, extracted in 50% IPA for 30 min, or in 100% IPAfor 15 min then back to 50% IPA for 30 min, DI water for 30 min andfinally in PBS saline overnight. Inspected lens is packaged in lenspackages containing a phosphate buffered saline (pH˜7.2) and autoclavedat 121° C. for about 30-45 minutes.

Example 3

A lens formulation is purged with nitrogen at room temperature for 30 to35 minutes. The N₂-purged lens formulation is introduced intopolypropylene molds and cured by UV/visible light (Hamamatsu lamp) for acuring time period. The post cast molding procedures described inExample 2 are used in this process for producing SiHy contact lenses.

Examples 4-24

In Examples 4 to 24, polymerizable compositions are prepared and listedin Tables 1-4. All the concentrations of the components listed in thetables are weight part units. The prepared polymerizable compositionscomprises 0.01 weight part of a reactive dye (RB246 or RB247) and 0.5weight part of free radical initiator (either VAZO 64 for thermallycurable compositions or DC1173 for UV-curable compositions).

TABLE 1 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 1^(st) mPDMS 40 (mSi1) 33(mSi1) 33 (mSi2) 30 (mSi1) 26 (mSi1) 40 (mSi2) Si Macromer 5 (CE- 10(CE- 10 (CE- 14 (CE- 17 (CE- 5 (CE- PDMS) PDMS) PDMS) PDMS) PDMS) PDMS)NVP 43 40 40 44 43 43 MMA 10 15 15 10 15 10 TEGDMA 0.2 0.2 0.2   0.2 0.20.2 Solvent 0 0 0 6 (TAA) 0 0 Curing 55/70/100° C. 55/70/100° C.55/70/100° C. 55/70/100° C. 55/70/100° C. 55/70/100° C. Profile 4 h/4h/1 h 4 h/4 h/1 h 4 h/4 h/1 h 4 h/4 h/1 h 4 h, 4 h, 1 h 4 h/4 h/1 hExtraction IPA IPA IPA IPA IPA IPA Medium

TABLE 2 Ex. 10 Ex. 11 Ex. 12 Ex. 13* Ex. 14 Ex. 15 1^(st) mPDMS 26(mSi2) 35 (mSi1) 37 (mSi2) 18 (mSi2) 34 (D6) 22 (D3) 2^(nd) mPDMS 0 0 016 (mSi1) 0 0 Si Macromer 17 (CE- 5 (CE- 3 (betacon) 5 (betacon) 6 (GA)25 (G1) PDMS) PDMS) NVP 40 48 50 50 40 43 MMA 15 10 10 5 10 10 TEGDMA0.2 0.2 0.5 1 0.2 0.2 HEMA 0 0 0 0 0.2 0 TEGDVE 0 0 0.1 0.1 0 0 Norbloc0.9 0.9 0.9 0.9 0.9 2 Solvent 10 (1-hexanol) 10 (PrOH) 0 0 3 (TAA) 0Curing 55/70/100° C. 55/70/100° C. 55/80/100° C. 55/80/100° C.55/80/100° C.; 55/80/100° C. Profile 4 hr/4 hr/1 hr 4 hr/4 hr/1 hr (40min/)₂40 min (40 min/)₂40 min (30 min/)₂30 min 1 hr/1 hr/1 hr ExtractionIPA IPA IPA; & aqueous IPA, & aqueous H2O; & IPA IPA medium *alsocontains 5 weight part units of methoxy ethyleneglycol methacrylate.

TABLE 3 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 1st mPDMS 25 (D3) 35(D3) 33 (mSi1) 25 (mSi1) 30 (D9) 35 (D6) Si Macromer 25 (G1) 10 (G1) 4(LMW- 25 (GA)   16 (G3) 12 (G1) CEPDMS) NVP 40 48 53 40 45 46 MMA 10 710 10 7 7 TEGDMA 0.2 0.2 0.2 0.2 0.2 0.2 Norbloc 2 2 2 2 2 2 Solvent 0 00 0 7 (TAA) 3 (TAA) Curing 55/80/100° C. 55/80/100° C. 55/80/100° C.55/80/100° C. 55/80/100° C. 55/80/100° C. Profile 1 hr/1 hr/1 hr 1 hr/1hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hrExtraction IPA IPA H₂O IPA IPA IPA medium

TABLE 4 Ex. 22 Ex. 23 Ex. 24 1st mPDMS 18 (mSi2) 18 (mSi2) 36.5 (D3) 2ndmPDMS 16 (mSi1) 16 (mSi1) 0 Si Macromer 5 5 (LMW- 7.7 (CE- (betacon)CEPDMS) PDMS) NVP 50 50 43.8 MMA 5 5 10 TEGDMA 1 1 0 DMA 0.1 0.1 0Initiator 0.5 0.5 0.5 (DC1173) (DC1173) (VAZO 64) Curing 5 mW/cm² 5mW/cm² 55/70/100° C. Profile 30 min 30 min 4 hr/4 hr/1 hr ExtractionIPA; & IPA; & IPA medium aqueous aqueous

SiHy contact lenses are prepared from those polymerizable compositionsaccording to curing processes described in Example 2 or 3. The lensproperties of resultant SiHy contact lenses are determined according toprocedure described in Example 1 and reported in Table 5.

TABLE 5 [NVA] mmol [H-D] meq Dk EWC Modulus WBUT WCA_(CB) [Si comp] g[NVA] g (Barrers) (%) (MPa) (s) (°) Ex. 4 8.6 0.078 NA NA NA 2 NA Ex. 58.4 0.17 NA NA NA 1 NA Ex. 6 8.4 0.17 NA NA NA 1 NA Ex. 7 9.0 0.21 106NA 0.79 10 NA Ex. 8 9.0 0.26 NA NA NA 5 NA Ex. 9 8.6 0.078 NA NA NA 5 NAEx. 10 8.4 0.28 NA NA NA 5 NA Ex. 11 10.8 0.07 NA NA NA <1 NA Ex. 1211.2 0.072 NA   50.8 1.11 3~5 NA Ex. 13 11.5 0.10 NA NA NA 0~2 NA Ex. 149.0 0.18  85 49 0.69 15 NA Ex. 15 8.2 1.05 106 44 NA <5 NA Ex. 16 7.21.13 120 41 NA <1 NA Ex. 17 9.6 0.38 113 48 0.77 10 54 Ex. 18 12.9 0.075 88 0.6  5 55 Ex. 19 7.2 0.75 117 40 1.2  8 NA Ex. 20 8.8 0.64 126 540.66 30 44 Ex. 21 8.8 0.47 112 52 0.65 14 45 Ex. 22 11.5 0.12 NA NA 0.4415 25~40 Ex. 23 11.5 0.10 NA NA NA 15 40 Ex. 24 8.9 0.12 85 50 0.56 1164 NVA: N-vinyl amide monomer(s); H-D: H-donor moieties; Si-comp: allsilicone-containing polymerizable component.

As shown in Table 5, there are two limitations on the amounts of thesiloxane-containing vinylic monomer, the polysiloxane vinyliccrosslinker and the N-vinyl amide monomer in a polymerizable compositionfor forming inherently wettable SiHy contact lenses.

The first limitation appears to be that there is a threshold amount ofthe N-vinyl amide monomer relative to the total amount of allsilicone-containing polymerizable components. That threshold value ofthe amount of the N-vinyl amide monomer is likely around 8.8 mmoles pergram of all the silicone-containing polymerizable components. In orderto form inherently wettable SiHy contact lenses, a polymerizablecomposition should comprise about 8.8 mmoles or more per gram of allsilicone-containing polymerizable components present in thepolymerizable composition.

The second limitation appears to be that there is also a threshold valuefor the total amount of the H-donor moieties (“H-D”) contributed by thepolysiloxane vinylic crosslinker and the siloxane-containing vinylicmonomer relative to the amount of the N-vinyl amide monomer. Thatthreshold value appears to be around 0.11 meqs of H-donor moieties pergram of the N-vinyl amide monomer. In order to form inherently wettableSiHy contact lenses, a polymerizable composition should comprise about0.11 meqs or more of H-donor moieties (contributed from all thesilicone-containing polymerizable components) per gram of the N-vinylamide monomer.

Examples 25-76

In Examples 25 to 76, polymerizable compositions are prepared and listedin Tables 6α-6h. All the concentrations of the components listed in thetables are weight part units. The prepared polymerizable compositionscomprises 0.01 weight part of a reactive dye (RB246 or RB247) and 0.5weight part of free radical initiator (either VAZO 64 for thermallycurable compositions or DC1173 for UV-curable compositions).

TABLE 6a Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 mPDMS 25 (mSi1) 23(D3) 35 (D3) 35 (D3) 35 (D3) 35 (D3) Si macromer 20 (G3)   18 (G3) 10(G0) 10 (G1) 10 (G1) 10 (G1) NVP 46 50 48 48 48 48 MMA 7 7 7 7 7 7TEGDMA 0.2 0.2 0.2 0.2 0.2 0.2 TEGDVE 0 0 0 0 0.05 0.1 Norbloc 2 2 2 2 22 TAA 5 NA 10 0 0 0 Curing 55/80/100° C. 55/80/100° C. 55/80/100° C.55/80/100° C. 55/80/100° C. 55/80/100° C. Profile 1 hr/1 hr/1 hr 1hr/1hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hrExtraction IPA IPA IPA IPA IPA IPA medium

TABLE 6b Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35 Ex. 36 mPDMS 35 (D6) 35 (D6)35 (D6) 35 (mSi1) 35 (mSi1) 35 (mSi1) Si macromer 12 (G1) 12 (G1) 12(G1) 10 (G1)   10 (G1)   10 (G1)   NVP 46 46 46 48 48 48 MMA 7 7 7 7 7 7TEGDMA 0.2 0.2 0.2 0.1 0.1 0.1 Norbloc 2 2 2 1.8 1.8 2 TAA 3 3 3 0 0 10Curing 55/80/100° C. 55/70/100° C. 55/70/100° C. 55/80/100° C.55/90/100° C. 55/70/100° C. Profile 1 hr/2 hr/1 hr 4 hr/4 hr/1 hr 4 hr/4hr/2 hr 2 hr/2 hr/2 hr 1 hr/1 hr/1 hr 4 hr/4 hr/2 hr Extraction IPA IPAIPA IPA IPA IPA medium

TABLE 6c Ex. 37 Ex. 38 Ex. 39 Ex. 40 Ex. 41 Ex. 42 Ex. 43 mPDMS 30(mSi1) 30 (mSi1) 30 (D9) 30 (D9) 23 (D9) 30 (D9) 30 (D9) Si macromer 15(G1)   15 (G1)   16 (G3) 16 (G3) 20 (G3) 16 (G3) 16 (G3) NVP 48 48 45 4548 45 45 MMA 7 7 7 7 7 7 7 TEGDMA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 HEMA 0 0 00 0 1 0 DMA 0 0 0 2 2 0 0 Norbloc 2 2 2 2 2 2 2 UV28 0 0 0 0 0 0 0.4 TAA0 0 9 9 5 9 9 Curing 55/80/100° C. 55/70/100° C. 55/80/100° C.55/80/100° C. 55/80/100° C. 55/80/100° C. 55/80/100° C. Profile 1 hr/2hr/1 hr 4 hr/4 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1hr/1 hr/1 hr 1 hr/1 hr/1 hr Extraction IPA IPA IPA IPA IPA IPA IPAmedium

TABLE 6d Ex. 44 Ex. 45 Ex. 46 Ex. 47 Ex. 48 Ex. 49 Ex. 50 mPDMS 30 (D9)27 (D9) 27 (D9) 27 (D9) 27 (D6) 27 (D6) 27 (D6) Si macromer 16 (G4) 16(G4) 16 (G4) 16 (G4) 16 (G4) 16 (G4) 16 (G4) NVP 45 48 48 48 48 48 48MMA 7 7 7 7 7 7 7 TEGDMA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 HEMA 0 0 0 1 0 0 1DMA 0 0 2 0 0 2 0 Norbloc 2 2 2 2 2 2 2 TAA 9 10 10 10 3 3 3 Curing55/80/100° C. 55/80/100° C. 55/80/100° C. 55/80/100° C. 55/80/100° C.55/80/100° C. 55/80/100° C. Profile 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hr 1 hr/1 hr/1 hrExtraction IPA IPA IPA IPA IPA IPA IPA medium

TABLE 6e Ex. 51 Ex. 52 Ex. 53 Ex. 54 Ex. 55 Ex. 56 Ex. 57 mPDMS 27 (D9)23 (D6) 23 (D6) 27 (mSi1) 27 (D9) 33 (D9) 33 (D9) Si macromer 16 (G4) 20(G4) 20 (G4) 16 (G4)   16 (G4) 10 (G4) 10 (G4) NVP 48 48 48 48 48 46 46MMA 7 7 7 7 7 10 10 TEGDMA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 DMA 0 0 2 0 0 0 0Norbloc 1.8 2 2 2 1.8 1.5 1.5 UV28 0 0 0 0 0 0.26 0.26 TAA 3 3 3 10 1010 10 Curing 55/80/100° C. 55/80/100° C. 55/80/100° C. 60/80/100° C.55/80/100° C. 55/80/100° C. 55/80/100° C. Profile 30 min/2 hr/ 1 hr/1hr/ 1 hr/1 hr/ 2.5 hr/2.5 hr/ 30 min/2 hr/ 30 min/2 hr/ 40 min/40 min/30 min 1 hr 1 hr 1 hr 30 min 30 min 40 min Extraction IPA IPA IPA IPAIPA IPA IPA medium

TABLE 6f Ex. 58 Ex. 59 Ex. 60 Ex. 61 Ex. 62 Ex. 63 Ex. 64 mPDMS 30 (D9)35 (D6) 33 (D6) 27 (D9) 33 (D9) 33 (D9) 33 (D9) Si macromer 10 (G4) 12(G1) 11 (G4) 16 (G4) 10 (G4) 10 (G4) 10 (G4) NVP 46 46 46 48 46 46 46MMA 13 10.5 11 7 10 10 10 TEGDMA 0.2 0.1 0.65 0.2 0.2 0.65 0.2 Norbloc1.5 1.5 1.5 1.8 1.8 1.5 1.5 UV28 0.26 0.26 0.4 0 0 0.4 0.35 TAA 10 8 1010 10 10 10 Curing 55/80/100° C. 55/80/100° C. 55/80/100° C. 55/80/100°C. 55/80/100° C. 55/80/100° C. 55/80/100° C. Profile 40 min/40 min/ 40min/40 min/ 30 min/120 min/ 30 min/120 min/ 30 min/120 min/ 30 min/120min/ 30 min/120 min/ 40 min 40 min 30 min 30 min 30 min 30 min 30 minExtraction IPA IPA IPA IPA IPA IPA IPA medium

TABLE 6g Ex. 65 Ex. 66 Ex. 67 Ex. 68 Ex. 69 Ex. 70 mPDMS 30 (D9) 30 (D9)35 (D6) 35 (D6) 37 (D6) 34 (1667B) Si macromer 10 (G4) 10 (G4) 12 (G1)12 (G1) 10 (G1) 6 (GA)   NVP 46 46 46 0 0 40 VMA 0 0 0 45 45 0 MMA 13 1310.5 8 8 9 TEGDMA 0.2 0.2 0.1 0.1 0.1 0.4 HEMA 0 0 0 0 0 0.4 Norbloc 1.81.5 1.8 0 0 1.8 UV28 0 0.26 0 0 0 0 TAA 10 10 8 0 0 3 Curing 55/80/100°C. 55/80/100° C. 55/70/100° C. 55/70/100° C. 55/70/100° C. 55/80/100° C.Profile 0.67 hr/0.67 hr/ 0.67 hr/0.67 hr/ 4 hr/4 hr/1 hr 4 hr/4 hr/1 hr4 hr/4 hr/1 hr 30 min/30 min/ 0.67 hr 0.67 hr 30 min Extraction IPA IPAIPA IPA IPA H2O; IPA medium

TABLE 6h Ex. 71 Ex. 72 Ex. 73 Ex. 74 Ex. 75 Ex. 76 mPDMS 33 (D9) 33 (D9)33 (D9) 33 (D9) 33 (D9) 33 (D9) Si macromer 10 (G4) 10 (G4) 10 (G4) 10(G4) 10 (G4) 10 (G4) NVP 0 0 24 32 0 0 VMA 42 42 20 12 42 42 MMA 14 1412 12 14 14 TEGDMA 0.65 0.65 0.65 0.65 0.65 0.65 HEMA 0 1 0 0 3 5Norbloc 1.5 1.5 1.5 1.5 1.5 1.5 UV28 0.4 0.4 0.4 0.4 0.4 0.4 TAA 10 1010 10 10 10 Curing 55/80/100° C. 55/80/100° C. 55/80/100° C. 55/80/100°C. 55/80/100° C. 55/80/100° C. Profile 40 min/40 min/ 40 min/40 min/ 40min/40 min/ 40 min/40 min/ 40 min/40 min/ 40 min/40 min/ 40 min 40 min40 min 40 min 40 min 40 min Extraction IPA IPA IPA IPA IPA IPA medium

SiHy contact lenses are prepared from those polymerizable compositionsaccording to curing processes described in Example 2 or 3. The lensproperties of resultant SiHy contact lenses are determined according toprocedure described in Example 1 and reported in Table 7.

TABLE 7 [NVA] mmol [H-D] meq Dk EWC Modulus WBUT WCA_(CB) [Si comp] g[NVA] g (barrers) (%) (MPa) (s) (°) Ex. 25 9.2 0.78 104 53 0.67 25 44Ex. 26 11.0 0.65 83 56 0.54 14 48 Ex. 27 9.6 0.38 108 50 0.72 NA 49 Ex.28 9.6 0.38 113 48 NA 14 55 Ex. 29 9.6 0.38 111 48 NA 17 52 Ex. 30 9.60.38 110 49 NA 17 54 Ex. 31 8.8 0.47 112 50 0.65 11 49 Ex. 32 8.8 0.47109 50 0.73 20 47 Ex. 33 8.8 0.47 102 NA 0.74 23 45 Ex. 34 9.6 0.38 92NA 0.73 53 51 Ex. 35 9.6 0.38 91 NA 0.71 78 61 Ex. 36 9.6 0.38 102 520.64 42 Ex. 37 9.6 0.56 115 50 0.73 11 49 Ex. 38 9.6 0.56 114 50 0.73 1546 Ex. 39 8.8 0.64 127 0.59 43 44 Ex. 40 8.8 0.64 165 0.52 48 44 Ex. 4110.0 0.75 102 0.58 45 54 Ex. 42 8.8 0.64 162 0.62 49 47 Ex. 43 8.8 0.64127 53 NA NA 44 Ex. 44 8.8 0.64 130 NA 0.82 65 40 Ex. 45 10.0 0.60 1450.79 51 41 Ex. 46 10.0 0.60 135 0.7  55 43 Ex. 47 10.0 0.60 132 0.73 4941 Ex. 48 10.0 0.60 111 0.85 44 49 Ex. 49 10.0 0.60 108 0.74 51 51 Ex.50 10.0 0.60 99 0.85 54 50 Ex. 51 10.0 0.60 118 54 0.59 54 46 Ex. 5210.0 0.75 116 0.84 36 NA Ex. 53 10.0 0.75 108 NA 0.74 51 51 Ex. 54 10.00.60 115 0.73 62 46 Ex. 55 10.0 0.60 115 54 0.67 22 42 Ex. 56 9.6 0.39114 57 0.45 23 52 Ex. 57 9.6 0.39 114 56 0.47 23 49 Ex. 58 10.3 0.39 10258 0.47 21 53 Ex. 59 8.8 0.47 107 52 0.54 21 55 Ex. 60 10.0 0.60 109 NA0.62 NA 50 Ex. 61 9.6 0.39 111 54 0.67 22 42 Ex. 62 10.0 0.53 118 550.5  23 47 Ex. 60 9.4 0.43 109 NA 0.65 NA 50 Ex. 64 9.6 0.39 53 0.51 3052 Ex. 65 10.3 0.39 106 55 0.48 21 54 Ex. 66 10.3 0.39 57 0.5  30 53 Ex.67 8.8 0.47 119 51 0.65 21 51 Ex. 68 9.7 0.48 61 0.7  60 Ex. 69 9.7 0.4060 60 Ex. 70 9.0 0.27 85.5 50 0.6  25 NA Ex. 71 9.9 0.43 121 53 0.67 5358 Ex. 72 9.9 0.43 118 53 0.67 56 54 Ex. 73 9.7 0.41 NA 54 0.63 61 50Ex. 74 9.5 0.41 NA 53 0.64 62 49 Ex. 75 9.9 0.43 NA 53 0.69 65 50 Ex. 769.9 0.43 NA 52 0.71 65 53

Table 7 shows that when a polymerizable composition comprises at least8.8 mmoles of N-vinyl amide monomer(s) (NVP and/or VMA) per gram of thesum of the siloxane-containing vinylic monomer and the polysiloxanevinylic crosslinker and greater than 0.11 meqs of the H-donor moieties(i.e., hydroxyl groups of the polysiloxane vinylic crosslinker) per gramof N-vinyl amide monomer(s) (NVP and/or VMA), the resultant SiHy lensesprepared from such a composition are inherently wettable.

Example 74

The surface compositions of SiHy contact lenses are determined bycharacterizing vacuum dried contact lenses with X-ray photoelectronspectroscopy (XPS). XPS is a method for measuring the surfacecomposition of lenses with a sampling depth of about 10 nm.

XPS analysis of SiHy contact lenses of the invention (prepared accordingto the procedures described in Examples 21 and 56) and commercial SiHycontact lenses without plasma treatment or any coating (ACUVUE®Advance®, MyDay, CLARITI™, AVAIRA, ACUVUE® TruEye™, Oasys®, Ultra™,Biofinity® are carried out. All lenses are vacuum-dried. Polyethylenesheets (Goodfellow, LDPE, d=0.015 mm) and DAILIES® AquaComfortPlus(DACP) are used as control because they do not contain silicon. Thesurface compositions of SiHy contact lenses are reported in Table 8below.

TABLE 8 Dk Atomic percentage by XPS H₂O % (barrers) C N O F Si N/SiPolyethylene control 82.9 2.2 12.4 0.9 1.7 Dailies ® 55.8 2.2 37.7 1.52.7 AquaComfortPlus ® Advance ® 47 65 61.1 4.9 24.9 0.7 8.4 0.58Clariti ™ 56 60 57.4 4.8 26.6 0.9 10.3 0.47 MyDay ™ 54 80 61.3 3.4 26.9nm 8.4 0.41 AVAIRA ® 46 100 52.4 2.5 27.8 4.2 13.1 0.19 TruEye ® 46 10058.1 4.9 29 1 6.9 0.71 Oasys ® 38 103 54.5 4.4 30.9 0.8 9.4 0.47 Example21 52 112 57.7 4.6 25.4 0.7 11.7 0.39 Example 53 57 114 59.9 4.6 24.80.5 10.2 0.45 Ultra ™ 46 114 59.2 3.3 24.2 0.6 12.7 0.26 Biofinity ® 48128 43.1 2.1 30.7 4.8 19.3 0.11

The low value of Si % for the two control samples and the observedfluorine content in the non-fluorine-containing lenses indicate somecontaminants which could be introduced during the preparation processincluding vacuum drying process and XPS analysis. The values of atomicSi percentage for control samples may represent the base line of XPSanalysis.

All the publications, patents, and patent application publications,which have been cited herein above in this application, are herebyincorporated by reference in their entireties.

What is claimed is:
 1. A silicone hydrogel contact lens, comprising asilicone hydrogel bulk material which comprises: (1) first repeatingunits of at least one siloxane-containing vinylic monomer including 0 to10 first H-donor moieties, (2) second repeating units of at least onefirst polysiloxane vinylic crosslinker which has second H-donor moietiesand is a compound of formula (A)

in which ν1 is an integer of from 30 to 500 and ω1 is an integer of from1 to 75, provided that ω1/ν1 is from 0.035 to 0.15, wherein the compoundof formula (A) has a number average molecular weight of from 3000Daltons to 80,000 Daltons; (3) third repeating units of at least onehydrophilic N-vinyl amide monomer, and (4) optionally fourth repeatingunits of at least one second polysiloxane vinylic crosslinker having 0to 35 fourth H-donor moieties, wherein the second repeating units ofsaid at least one first polysiloxane vinylic crosslinker are differentfrom the fourth repeating units of said at least one second polysiloxanevinylic crosslinkers, wherein the first, second, and fourth H-donormoieties independent of one another are hydroxyl groups, carboxylgroups, amino groups of —NHR^(o), amino linkages of —NH—, amide linkagesof —CONH—, urethane linkages of —OCONH—, or combinations thereof,wherein R^(o) is H or a C₁-C₄ alkyl, wherein the silicone hydrogel bulkmaterial comprises at least 8.8 mmoles of the third repeating units pergram of all the first, second and fourth repeating units in total and atleast 0.11 meqs of all the first, second, and fourth H-donor moieties intotal per gram of the third repeating units, wherein the siliconehydrogel contact lens has an oxygen permeability of at least 50 barrers,an elastic modulus of from 0.2 MPa to 1.5 MPa, and an equilibrium watercontent of from 40% to 70% by weight and is inherently wettable ascharacterized by having a water-break-up-time of at least 10 seconds anda water contact angle by captive bubble of 80 degrees or less withoutbeing subjected to any post-curing surface treatment.
 2. The siliconehydrogel contact lens of claim 1, wherein the silicone hydrogel bulkmaterial comprises at least 9.0 mmole of the third repeating units pergram of all the first, second and fourth repeating units in total. 3.The silicone hydrogel contact lens of claim 1, wherein the siliconehydrogel bulk material comprises at least 9.2 mmole of the thirdrepeating units per gram of all the first, second and fourth repeatingunits in total.
 4. The silicone hydrogel contact lens of claim 1,wherein the silicone hydrogel bulk material comprises at least 9.6 mmoleof the third repeating units per gram of all the first, second andfourth repeating units in total.
 5. The silicone hydrogel contact lensof claim 1, wherein the silicone hydrogel bulk material comprises atleast 0.15 meqs of all the first, second, and fourth H-donor moieties intotal per gram of the third repeating units.
 6. The silicone hydrogelcontact lens of claim 1, wherein the silicone hydrogel bulk materialcomprises at least 0.20 meqs of all the first, second, and fourthH-donor moieties in total per gram of the third repeating units.
 7. Thesilicone hydrogel contact lens of claim 1, wherein the silicone hydrogelbulk material comprises at least 0.25 meqs of all the first, second, andfourth H-donor moieties in total per gram of the third repeating units.8. The silicone hydrogel contact lens of claim 1, wherein the siliconehydrogel contact lens has a water-break-up-time of at least 15 secondswithout being subjected to any post-curing surface treatment.
 9. Thesilicone hydrogel contact lens of claim 1, wherein the silicone hydrogelcontact lens has a water-break-up-time of at least 20 seconds withoutbeing subjected to any post-curing surface treatment.
 10. The siliconehydrogel contact lens of claim 1, wherein the silicone hydrogel contactlens has a water contact angle by captive bubble of 75 degrees or lesswithout being subjected to any post-curing surface treatment.
 11. Thesilicone hydrogel contact lens of claim 1, wherein the silicone hydrogelcontact lens has a water contact angle by captive bubble of 70 degreesor less without being subjected to any post-curing surface treatment.12. The silicone hydrogel contact lens of claim 1, wherein the siliconehydrogel contact lens has a water contact angle by captive bubble of 65degrees or less without being subjected to any post-curing surfacetreatment.
 13. The silicone hydrogel contact lens of claim 1, whereinthe siloxane-containing vinylic monomer is amono-(meth)acryloyl-terminated, monoalkyl-terminated polysiloxane offormula (I)

in which: R_(o) is H or methyl; X_(o) is O or NR₁; L₁ is a C₃-C₈alkylene divalent radical or a divalent radical of

L₁′ is a C₂-C₈ alkylene divalent radical which has zero or one hydroxylgroup; L₁″ is C₃-C₈ alkylene divalent radical which has zero or onehydroxyl group; X₁ is O, NR₁, NHCOO, OCONH, CONR₁, or NR₁CO; R₁ is H ora C₁-C₄ alkyl having 0 to 2 hydroxyl group; R_(t1) is a C₁-C₄ alkyl; X₁′is O or NR₁; q1 is an integer of 1 to 20; q2 is an integer of 0 to 20;n1 is an integer of 3 to
 25. 14. The silicone hydrogel contact lens ofclaim 13, wherein the siloxane-containing vinylic monomer isα-(meth)acryloxypropyl terminated ω-butyl (or ω-methyl) terminatedpolydimethylsiloxane, α-(meth)acryloxy-2-hydroxypropyloxypropylterminated ω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(2-hydroxyl-methacryloxypropyloxy-propyl)-ω-butyl-decamethylpentasiloxane,α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxy-propylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(meth)acryloxy-(polyethylenoxy)-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-butyl(or ω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-terminated ω-butyl (orω-methyl) terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyloxy(polyethylenoxy)propyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-(meth)acryloylamidopropyloxypropyl terminated ω-butyl (or ω-methyl)terminated polydimethylsiloxane,a-N-methyl-(meth)acryloylamidopropyloxy-propyl terminated ω-butyl (orω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl(or ω-methyl) polydimethylsiloxane,α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminatedw-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,α-[3-(meth)acryloylamido-2-hydroxypropyloxypropyl]terminated ω-butyl (orω-methyl) polydimethylsiloxane,α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl] terminatedω-butyl (or ω-methyl) terminated polydimethylsiloxane,N-methyl-N′-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide,N-(2,3-dihydroxypropane)-N′-(propyltetra(dimethylsiloxy)-dimethylbutylsilane)(meth)acrylamide,(meth)acryloylamidopropyltetra(dimethylsiloxy)-dimethylbutylsilane, or amixture thereof.
 15. The silicone hydrogel contact lens of claim 13,wherein the hydrophilic N-vinyl amide monomer is N-vinylpyrrolidone,N-vinyl piperidone, N-vinyl caprolactam, N-vinyl-N-methyl acetamide,N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide,N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethylformamide, and mixtures thereof.
 16. The silicone hydrogel contact lensof claim 15, wherein the silicone hydrogel contact lens furthercomprises repeating units of one or more non-silicone vinyliccrosslinking agents.
 17. The silicone hydrogel contact lens of claim 15,wherein the silicone hydrogel contact lens further comprises repeatingunits of a blending vinylic monomer.
 18. The silicone hydrogel contactlens of claim 15, wherein the silicone hydrogel contact lens furthercomprises repeating units of at least one UV-absorbing vinylic monomerand optionally repeating units of at least one UV/HEVL-absorbing vinylicmonomer.
 19. The silicone hydrogel contact lens of claim 18, wherein thesilicone hydrogel contact lens further comprises repeating units of2-[2′-hydroxy-5′-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole and atleast one UV/HEVL-absorbing vinylic monomer selected from the groupconsisting of2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole,2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole,and combinations thereof.
 20. The silicone hydrogel contact lens ofclaim 18, wherein the silicone hydrogel contact lens is characterized byhaving the UVB transmittance of 10% or less between 280 and 315nanometers and a UVA transmittance of 30% or less between 315 nm and 380nm and a Violet transmittance of 70% or less between 380 nm and 440 nm.21. The silicone hydrogel contact lens of claim 15, wherein the siliconehydrogel contact lens further comprises repeating units of one or morehydrophilic acrylic monomers selected from the group consisting ofN,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-hydroxylethyl(meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl(meth)acrylate, glycerol methacrylate, polyethylene glycol(meth)acrylate having a number average molecular weight of up to 1500,polyethylene glycol C₁-C₄-alkyl ether (meth)acrylate having a numberaverage molecular weight of up to 1500,N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid,ethylacrylic acid, and combinations thereof.
 22. The silicone hydrogelcontact lens of claim 16, wherein the silicone hydrogel contact lensfurther comprises repeating units of a blending vinylic monomer.
 23. Thesilicone hydrogel contact lens of claim 16, wherein the siliconehydrogel contact lens further comprises repeating units of at least oneUV-absorbing vinylic monomer and optionally repeating units of at leastone UV/HEVL-absorbing vinylic monomer.
 24. The silicone hydrogel contactlens of claim 23, wherein the silicone hydrogel contact furthercomprises repeating units of2-[2′-hydroxy-5′-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole and atleast one UV/HEVL-absorbing vinylic monomer selected from the groupconsisting of2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole,2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole,and combinations thereof.
 25. The silicone hydrogel contact lens ofclaim 23, wherein the silicone hydrogel contact lens is characterized byhaving the UVB transmittance of 10% or less between 280 and 315nanometers and a UVA transmittance of 30% or less between 315 nm and 380nm and a Violet transmittance of 70% or less between 380 nm and 440 nm.26. The silicone hydrogel contact lens of claim 16, wherein the siliconehydrogel contact lens further comprises repeating units of one or morehydrophilic acrylic monomers selected from the group consisting ofN,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-hydroxylethyl(meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl(meth)acrylate, glycerol methacrylate, polyethylene glycol(meth)acrylate having a number average molecular weight of up to 1500,polyethylene glycol C₁-C₄-alkyl ether (meth)acrylate having a numberaverage molecular weight of up to 1500,N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid,ethylacrylic acid, and combinations thereof.
 27. The silicone hydrogelcontact lens of claim 17, wherein the silicone hydrogel contact lensfurther comprises repeating units of at least one UV-absorbing vinylicmonomer and optionally repeating units of at least one UV/HEVL-absorbingvinylic monomer.
 28. The silicone hydrogel contact lens of claim 27,wherein the silicone hydrogel contact lens further comprises repeatingunits of 2-[2′-hydroxy-5′-(2-methacryloxyethyl)phenyl)]-2H-benzotriazoleand at least one UV/HEVL-absorbing vinylic monomer selected from thegroup consisting of2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole,2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole,and combinations thereof.
 29. The silicone hydrogel contact lens ofclaim 27, wherein the silicone hydrogel contact lens is characterized byhaving the UVB transmittance of 10% or less between 280 and 315nanometers and a UVA transmittance of 30% or less between 315 nm and 380nm and a Violet transmittance of 70% or less between 380 nm and 440 nm.30. The silicone hydrogel contact lens of claim 17, wherein the siliconehydrogel contact lens further comprises repeating units of one or morehydrophilic acrylic monomers selected from the group consisting ofN,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-hydroxylethyl(meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl(meth)acrylate, glycerol methacrylate, polyethylene glycol(meth)acrylate having a number average molecular weight of up to 1500,polyethylene glycol C₁-C₄-alkyl ether (meth)acrylate having a numberaverage molecular weight of up to 1500,N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid,ethylacrylic acid, and combinations thereof.